Diatomaceous energy storage devices

ABSTRACT

A printed energy storage device includes a first electrode, a second electrode, and a separator between the first and the second electrode. At least one of the first electrode, the second electrode, and the separator includes frustules, for example of diatoms. The frustules may have a uniform or substantially uniform property or attribute such as shape, dimension, and/or porosity. A property or attribute of the frustules can also be modified by applying or forming a surface modifying structure and/or material to a surface of the frustules. A membrane for an energy storage device includes frustules. An ink for a printed film includes frustules.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/803,653, filed Nov. 3, 2017, entitled “Diatomaceous Energy StorageDevices,” which is a continuation of U.S. patent application Ser. No.14/848,919, filed Sep. 9, 2015, entitled “Diatomaceous Energy StorageDevices, now U.S. Pat. No. 9,834,447, which is a continuation of U.S.patent application Ser. No. 13/944,211, filed Jul. 17, 2013, entitled“Diatomaceous Energy Storage Devices,” now U.S. Pat. No. 9,136,065,which claims the benefit of U.S. Provisional Patent Application Ser. No.61/750,757, filed Jan. 9, 2013, entitled “Diatomaceous Energy StorageDevices,” and U.S. Provisional Patent Application Ser. No. 61/673,149,filed Jul. 18, 2012, entitled “Diatomaceous Energy Storage Devices,”each of which is incorporated herein by reference in its entirety.

BACKGROUND Field

The present application relates to energy storage devices, andparticularly to energy storage devices comprising frustules of diatoms.

Description of the Related Art

Diatoms typically include unicellular eukaryotes, such as single-celledalgae. Diatoms are abundant in nature and can be found in both freshwater and marine environments. Generally, diatoms are enclosed by afrustule having two valves fitted together through a connective zonecomprising girdle elements. Diatomaceous earth, sometimes known asdiatomite, can be a source of frustules. Diatomaceous earth comprisesfossilized frustules and can be used in a diverse range of applications,including as a filtering agent, a filling agent for paints or plastics,an adsorbent, cat litter, or an abrasive material.

Frustules often comprise a significant amount of silica (SiO₂), alongwith alumina, iron oxide, titanium oxide, phosphate, lime, sodium,and/or potassium. Frustules are typically electrically insulating.Frustules may comprise a wide variety of dimensions, surface features,shapes, and other attributes. For example, frustules may comprisediverse shapes, including but not limited to cylinders, spheres, discs,or prisms. Frustules comprise a symmetrical shape or a non-symmetricalshape. Diatoms may be categorized according to the shape and/or symmetryof the frustules, for example grouping the diatoms based on existence orlack of radial symmetry. Frustules may comprise dimensions within arange from less than about one micron to about hundreds of microns.Frustules may also comprise varying porosity, having numerous pores orslits. Pores or slits of frustules may vary in shape, size, and/ordensity. For example, frustules may comprise pores having dimensionsfrom about 5 nm to about 1000 nm.

Frustules may comprise significant mechanical strength or resistance toshear stress, for example due to the dimensions of the frustule,frustule shape, porosity, and/or material composition.

SUMMARY

An energy storage device such as a battery (e.g., rechargeable battery),capacitor, and/or supercapacitor (e.g., electric double-layer capacitor(EDLC)), may be fabricated using frustules embedded in at least onelayer of the energy storage device. The frustules can be sorted to havea selected shape, dimension, porosity, material, surface feature, and/oranother suitable frustule attribute, which may be uniform orsubstantially uniform or which may vary. The frustules may include afrustule surface modifying structure and/or material. The energy storagedevice may include layers such as electrodes, separators, and/or currentcollectors. For example, a separator may be positioned between a firstelectrode and a second electrode, a first current collector may becoupled to the first electrode, and a second current collector may becoupled to the second electrode. At least one of the separator, thefirst electrode, and the second electrode may include the frustules.Inclusion of frustules in at least a portion of an energy storage devicecan help to fabricate the energy storage device using printingtechnology, including screen printing, roll-to-roll printing, ink-jetprinting, and/or another suitable printing process. The frustules canprovide structural support for an energy storage device layer and helpthe energy storage device layer to maintain a uniform or substantiallyuniform thickness during manufacturing and/or use. Porous frustules canallow unimpeded or substantially unimpeded flow of electrons or ionicspecies. Frustules including surface structures or material can increaseconductivity of a layer.

In some embodiments, a printed energy storage device comprises a firstelectrode, a second electrode, and a separator between the firstelectrode and the second electrode. At least one of the first electrode,the second electrode, and the separator includes frustules.

In some embodiments, the separator includes the frustules. In someembodiments, the first electrode includes the frustules. In someembodiments, the separator and the first electrode include thefrustules. In some embodiments, the second electrode includes thefrustules. In some embodiments, the separator and the second electrodeinclude the frustules. In some embodiments, the first electrode and thesecond electrode include the frustules. In some embodiments, theseparator, the first electrode, and the second electrode include thefrustules.

In some embodiments, the frustules have a substantially uniformproperty. In some embodiments, the property comprises shape, for exampleincluding a cylinder, a sphere, a disc, or a prism. In some embodiments,the property comprises a dimension, for example including diameter,length, or a longest axis. In some embodiments, the property comprisesporosity. In some embodiments, the property comprises mechanicalstrength.

In some embodiments, the frustules comprise a surface modifyingstructure. In some embodiments, the surface modifying structure includesa conductive material. In some embodiments, the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass. In some embodiments, the surface modifyingstructure includes zinc oxide (ZnO). In some embodiments, the surfacemodifying structure comprises a semiconductor. In some embodiments, thesemiconductor includes at least one of silicon, germanium, silicongermanium, and gallium arsenide. In some embodiments, the surfacemodifying structure comprises at least one of a nanowire, ananoparticle, and a structure having a rosette shape. In someembodiments, the surface modifying structure is on an exterior surfaceof the frustules. In some embodiments, the surface modifying structureis on an interior surface of the frustules. In some embodiments, thesurface modifying structure is on an interior surface and an exteriorsurface of the frustules.

In some embodiments, the frustules comprise a surface modifyingmaterial. In some embodiments, the surface modifying material comprisesa conductive material. In some embodiments, the surface modifyingmaterial includes at least one of silver, aluminum, tantalum, copper,lithium, magnesium, and brass. In some embodiments, the surfacemodifying material includes ZnO. In some embodiments, the surfacemodifying material includes a semiconductor. In some embodiments, thesemiconductor includes at least one of silicon, germanium, silicongermanium, and gallium arsenide. In some embodiments, the surfacemodifying material is on an exterior surface of the frustules. In someembodiments, the surface modifying material is on an interior surface ofthe frustules. In some embodiments, the surface modifying material is onan exterior surface and an interior surface of the frustules.

In some embodiments, the first electrode comprises a conductive filler.In some embodiments, the second electrode comprises a conductive filler.In some embodiments, the first electrode and the second electrodecomprise a conductive filler. In some embodiments, the conductive fillercomprises graphitic carbon. In some embodiments, the conductive fillercomprises graphene.

In some embodiments, the first electrode comprises an adherencematerial. In some embodiments, the second electrode comprises anadherence material. In some embodiments, the first electrode and thesecond electrode comprise an adherence material. In some embodiments,the separator comprises an adherence material. In some embodiments, thefirst electrode and the separator comprise an adherence material. Insome embodiments, the second electrode and the separator comprise anadherence material. In some embodiments, the first electrode, the secondelectrode, and the separator comprise an adherence material. In someembodiments, the adherence material comprises a polymer.

In some embodiments, the separator comprises an electrolyte. In someembodiments, the electrolyte comprises at least one of an ionic liquid,an acid, a base, and a salt. In some embodiments, the electrolytecomprises an electrolytic gel.

In some embodiments, the device comprises a first current collector inelectrical communication with the first electrode. In some embodiments,the device comprises a second current collector in electricalcommunication with the second electrode. In some embodiments, the devicecomprises a first current collector in electrical communication with thefirst electrode and a second current collector in electricalcommunication with the second electrode.

In some embodiments, the printed energy storage device comprises acapacitor. In some embodiments, the printed energy storage devicecomprises a supercapacitor. In some embodiments, the printed energystorage device comprises a battery.

In some embodiments, a system comprises a plurality of the printedenergy storage devices as described herein stacked on top of each other.In some embodiments, an electrical device comprises the printed energystorage devices described herein or the system.

In some embodiments, a membrane for a printed energy storage devicecomprises frustules.

In some embodiments, the frustules have a substantially uniformproperty. In some embodiments, the property comprises shape, for exampleincluding a cylinder, a sphere, a disc, or a prism. In some embodiments,the property comprises a dimension, for example including diameter,length, or a longest axis. In some embodiments, the property comprisesporosity. In some embodiments, the property comprises mechanicalstrength.

In some embodiments, the frustules comprise a surface modifyingstructure. In some embodiments, the surface modifying structure includesa conductive material. In some embodiments, the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass. In some embodiments, the surface modifyingstructure includes zinc oxide (ZnO). In some embodiments, the surfacemodifying structure comprises a semiconductor. In some embodiments, thesemiconductor includes at least one of silicon, germanium, silicongermanium, and gallium arsenide. In some embodiments, the surfacemodifying structure comprises at least one of a nanowire, ananoparticle, and a structure having a rosette shape. In someembodiments, the surface modifying structure is on an exterior surfaceof the frustules. In some embodiments, the surface modifying structureis on an interior surface of the frustules. In some embodiments, thesurface modifying structure is on an interior surface and an exteriorsurface of the frustules.

In some embodiments, the frustules comprise a surface modifyingmaterial. In some embodiments, the surface modifying material comprisesa conductive material. In some embodiments, the surface modifyingmaterial includes at least one of silver, aluminum, tantalum, copper,lithium, magnesium, and brass. In some embodiments, the surfacemodifying material includes ZnO. In some embodiments, the surfacemodifying material includes a semiconductor. In some embodiments, thesemiconductor includes at least one of silicon, germanium, silicongermanium, and gallium arsenide. In some embodiments, the surfacemodifying material is on an exterior surface of the frustules. In someembodiments, the surface modifying material is on an interior surface ofthe frustules. In some embodiments, the surface modifying material is onan exterior surface and an interior surface of the frustules.

In some embodiments, the membrane further comprises a conductive filler.In some embodiments, the conductive filler comprises graphitic carbon.In some embodiments, the conductive filler comprises graphene.

In some embodiments, the membrane further comprises an adherencematerial. In some embodiments, the adherence material comprises apolymer.

In some embodiments, the membrane further comprises an electrolyte. Insome embodiments, the electrolyte comprises at least one of an ionicliquid, an acid, a base, and a salt. In some embodiments, theelectrolyte comprises an electrolytic gel.

In some embodiments, an energy storage device comprises the membrane asdescribed herein. In some embodiments, the printed energy storage devicecomprises a capacitor. In some embodiments, the printed energy storagedevice comprises a supercapacitor. In some embodiments, the printedenergy storage device comprises a battery. In some embodiments, a systemcomprises a plurality of energy storage devices as described hereinstacked on top of each other. In some embodiments, an electrical devicecomprises the printed energy storage devices described herein or thesystem.

In some embodiments, a method of manufacturing a printed energy storagedevice comprises forming a first electrode, forming a second electrode,and forming a separator between the first electrode and the secondelectrode. At least one of the first electrode, the second electrode,and the separator includes frustules.

In some embodiments, the separator includes the frustules. In someembodiments, forming the separator includes forming a dispersion of thefrustules. In some embodiments, forming the separator includes screenprinting the separator. In some embodiments, forming the separatorincludes forming a membrane of the frustules. In some embodiments,forming the separator includes roll-to-roll printing the membraneincluding the separator.

In some embodiments, the first electrode includes the frustules. In someembodiments, forming the first electrode includes forming a dispersionof the frustules. In some embodiments, forming the first electrodeincludes screen printing the first electrode. In some embodiments,forming the first electrode includes forming a membrane of thefrustules. In some embodiments, forming the first electrode includesroll-to-roll printing the membrane including the first electrode.

In some embodiments, the second electrode includes the frustules. Insome embodiments, forming the second electrode includes forming adispersion of the frustules. In some embodiments, forming the secondelectrode includes screen printing the second electrode. In someembodiments, forming the second electrode includes forming a membrane ofthe frustules. In some embodiments, forming the second electrodeincludes roll-to-roll printing the membrane including the secondelectrode.

In some embodiments, the method further comprises sorting the frustulesaccording to a property. In some embodiments, the property comprises atleast one of shape, dimension, material, and porosity.

In some embodiments, an ink comprises a solution and frustules dispersedin the solution.

In some embodiments, the frustules have a substantially uniformproperty. In some embodiments, the property comprises shape, for exampleincluding a cylinder, a sphere, a disc, or a prism. In some embodiments,the property comprises a dimension, for example including diameter,length, or a longest axis. In some embodiments, the property comprisesporosity. In some embodiments, the property comprises mechanicalstrength.

In some embodiments, the frustules comprise a surface modifyingstructure. In some embodiments, the surface modifying structure includesa conductive material. In some embodiments, the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass. In some embodiments, the surface modifyingstructure includes zinc oxide (ZnO). In some embodiments, the surfacemodifying structure comprises a semiconductor. In some embodiments, thesemiconductor includes at least one of silicon, germanium, silicongermanium, and gallium arsenide. In some embodiments, the surfacemodifying structure comprises at least one of a nanowire, ananoparticle, and a structure having a rosette shape. In someembodiments, the surface modifying structure is on an exterior surfaceof the frustules. In some embodiments, the surface modifying structureis on an interior surface of the frustules. In some embodiments, thesurface modifying structure is on an interior surface and an exteriorsurface of the frustules.

In some embodiments, the frustules comprise a surface modifyingmaterial. In some embodiments, the surface modifying material comprisesa conductive material. In some embodiments, the surface modifyingmaterial includes at least one of silver, aluminum, tantalum, copper,lithium, magnesium, and brass. In some embodiments, the surfacemodifying material includes ZnO. In some embodiments, the surfacemodifying material includes a semiconductor. In some embodiments, thesemiconductor includes at least one of silicon, germanium, silicongermanium, and gallium arsenide. In some embodiments, the surfacemodifying material is on an exterior surface of the frustules. In someembodiments, the surface modifying material is on an interior surface ofthe frustules. In some embodiments, the surface modifying material is onan exterior surface and an interior surface of the frustules.

In some embodiments, the ink further comprises a conductive filler. Insome embodiments, the conductive filler comprises graphitic carbon. Insome embodiments, the conductive filler comprises graphene.

In some embodiments, the ink further comprises an adherence material. Insome embodiments, the adherence material comprises a polymer.

In some embodiments, the ink further comprises an electrolyte. In someembodiments, the electrolyte comprises at least one of an ionic liquid,an acid, a base, and a salt. In some embodiments, the electrolytecomprises an electrolytic gel.

In some embodiments, a device comprises at least one of the inksdescribed herein. In some embodiments, the device comprises a printedenergy storage device. In some embodiments, the printed energy storagedevice comprises a capacitor. In some embodiments, the printed energystorage device comprises a supercapacitor. In some embodiments, theprinted energy storage device comprises a battery.

A method of extracting a diatom frustule portion may comprise dispersinga plurality of diatom frustule portions in a dispersing solvent. Atleast one of an organic contaminant and an inorganic contaminant may beremoved. The method of extracting a diatom frustule portion may comprisedispersing the plurality of diatom frustule portions in a surfactant,the surfactant reducing an agglomeration of the plurality of diatomfrustule portions. The method may comprise extracting a plurality ofdiatom frustule portions having at least one common characteristic usinga disc stack centrifuge.

In some embodiments, the at least one common characteristic can includeat least one of a dimension, a shape, a material, and a degree ofbrokenness. The dimension may include at least one of a length and adiameter.

In some embodiments, a solid mixture can comprise the plurality ofdiatom frustule portions. The method of extracting a diatom frustuleportion may comprise reducing a particle dimension of the solid mixture.Reducing the particle dimension of the solid mixture may be beforedispersing the plurality of diatom frustule portions in the dispersingsolvent. In some embodiments, reducing the particle dimension cancomprise grinding the solid mixture. Grinding the solid mixture mayinclude applying to the solid mixture at least one of a mortar and apestle, a jar mill, and a rock crusher.

In some embodiments, a component of the solid mixture having a longestcomponent dimension that is greater than a longest frustule portiondimension of the plurality of diatom frustule portions can be extracted.Extracting the component of the solid mixture may comprise sieving thesolid mixture. Sieving the solid mixture may comprise processing thesolid mixture with a sieve having a mesh size from about 15 microns toabout 25 microns. Sieving the solid mixture may comprise processing thesolid mixture with a sieve having a mesh size from about 10 microns toabout 25 microns.

In some embodiments, the method of extracting a diatom frustule portioncan comprise sorting the plurality of diatom frustule portions toseparate a first diatom frustule portion from a second diatom frustuleportion, the first diatom frustule portion having a greater longestdimension. For example, the first diatom frustule portion may comprise aplurality of unbroken diatom frustule portions. The second diatomfrustule portion may comprise a plurality of broken diatom frustuleportions.

In some embodiments, sorting the plurality of diatom frustule portionscan comprise filtering the plurality of diatom frustule portions.Filtering may comprise disturbing agglomeration of the plurality ofdiatom frustule portions. In some embodiments, disturbing agglomerationof the plurality of diatom frustule portions can comprise stirring. Insome embodiments, disturbing agglomeration of the plurality of diatomfrustule portions can comprise shaking. In some embodiments, disturbingagglomeration of the plurality of diatom frustule portions can comprisebubbling.

Filtering may include applying a sieve to the plurality of diatomfrustule portions. For example, the sieve may have a mesh size fromabout 5 microns to about 10 microns, including about 7 microns.

In some embodiments, the method of extracting a diatom frustule portioncan include obtaining a washed diatom frustule portion. Obtaining thewashed diatom frustule portion may comprise washing the plurality ofdiatom frustule portions with a cleaning solvent after removing the atleast one of the organic contaminant and the inorganic contaminant. Insome embodiments, obtaining the washed diatom frustule portion cancomprise washing the diatom frustule portion having the at least onecommon characteristic with a cleaning solvent.

The cleaning solvent may be removed. For example, removing the cleaningsolvent may comprise sedimenting the plurality of diatom frustuleportions after removing at least one of the organic contaminant and theinorganic contaminant. For example, removing the cleaning solvent maycomprise sedimenting the plurality of diatom frustule portions havingthe at least one common characteristic. Sedimenting the plurality ofdiatom frustule portions may comprise centrifuging. In some embodiments,centrifuging can comprise applying a centrifuge suitable for large scaleprocessing. In some embodiments, centrifuging can comprise applying atleast one of a disc stack centrifuge, a decanter centrifuge, and atubular bowl centrifuge.

In some embodiments, at least one of the dispersing solvent and thecleaning solvent can comprise water.

In some embodiments, at least one of dispersing the plurality of diatomfrustule portions in the dispersing solvent and dispersing the pluralityof diatom frustule portions in the surfactant can comprise sonicatingthe plurality of diatom frustules.

The surfactant may comprise a cationic surfactant. For example, thecationic surfactant may comprise at least one of a benzalkoniumchloride, a cetrimonium bromide, a lauryl methyl gluceth-10hydroxypropyl dimonium chloride, a benzethonium chloride, a benzethoniumchloride, a bronidox, a dmethyldioctadecylammonium chloride, and atetramethylammonium hydroxide.

The surfactant may comprise a non-ionic surfactant. For example, thenon-ionic surfactant may comprise at least one of a cetyl alcohol, astearyl alcohol, a cetostearyl alcohol, an oleyl alcohol, apolyoxyethylene glycol alkyl ether, an octaethylene glycol monododecylether, a glucoside alkyl ethers, a decyl glucoside, a polyoxyethyleneglycol octylphenol ethers, an octylphenol ethoxylate (Triton X-100™), anonoxynol-9, a glyceryl laurate, a polysorbate, and a poloxamer.

In some embodiments, the method of extracting a diatom frustule portioncan comprise dispersing the plurality of diatom frustules in an additivecomponent. Dispersing the plurality of diatom frustules in an additivecomponent may be before dispersing the plurality of diatom frustules inthe surfactant. Dispersing the plurality of diatom frustules in anadditive component may be after dispersing the plurality of diatomfrustules in the surfactant. Dispersing the plurality of diatomfrustules in an additive component may be at least partiallysimultaneous with dispersing the plurality of diatom frustules in thesurfactant. The additive component may include at least one of apotassium chloride, an ammonium chloride, an ammonium hydroxide, and asodium hydroxide.

In some embodiments, dispersing the plurality of diatom frustuleportions can comprise obtaining a dispersion comprising about 1 weightpercent to about 5 weight percent of the plurality of diatom frustuleportions.

In some embodiments, removing the organic contaminant can compriseheating the plurality of diatom frustule portions in the presence of ableach. The bleach may include at least one of a hydrogen peroxide and anitric acid. Heating the plurality of diatom frustule portions maycomprise heating the plurality of diatom frustule portions in a solutioncomprising an amount of hydrogen peroxide in a range from about 10volume percent to about 20 volume percent. Heating the plurality ofdiatom frustule portions may comprise heating the plurality of diatomfrustule portions for a duration of about 5 minutes to about 15 minutes.

In some embodiments, removing the organic contaminant can compriseannealing the plurality of diatom frustule portions. In someembodiments, removing the inorganic contaminant can comprise combiningthe plurality of diatom frustule portions with at least one of ahydrochloric acid and a sulfuric acid. Combining the plurality of diatomfrustule portions with at least one of a hydrochloric acid and asulfuric acid may include mixing the plurality of diatom frustuleportions in a solution comprising about 15 volume percent to about 25volume percent of hydrochloric acid. For example, the mixing may be fora duration of about 20 minutes to about 40 minutes.

A method of extracting a diatom frustule portion may include extractinga plurality of diatom frustule portions having at least one commoncharacteristic using a disc stack centrifuge.

In some embodiments, the method of extracting a diatom frustule portioncan comprise dispersing the plurality of diatom frustule portions in adispersing solvent. In some embodiments, the method can compriseremoving at least one of an organic contaminant and an inorganiccontaminant. In some embodiments, the method can comprise dispersing theplurality of diatom frustule portions in a surfactant, the surfactantreducing an agglomeration of the plurality of diatom frustule portions.

The at least one common characteristic may include at least one of adimension, a shape, a material, and a degree of brokenness. Thedimension may include at least one of a length and a diameter.

In some embodiments, a solid mixture can comprise the plurality ofdiatom frustule portions. The method of extracting a diatom frustuleportion may comprise reducing a particle dimension of the solid mixture.Reducing the particle dimension of the solid mixture may be beforedispersing the plurality of diatom frustule portions in the dispersingsolvent. In some embodiments, reducing the particle dimension cancomprise grinding the solid mixture. Grinding the solid mixture mayinclude applying to the solid mixture at least one of a mortar and apestle, a jar mill, and a rock crusher.

In some embodiments, a component of the solid mixture having a longestcomponent dimension that is greater than a longest frustule portiondimension of the plurality of diatom frustule portions can be extracted.Extracting the component of the solid mixture may comprise sieving thesolid mixture. Sieving the solid mixture may comprise processing thesolid mixture with a sieve having a mesh size from about 15 microns toabout 25 microns. Sieving the solid mixture may comprise processing thesolid mixture with a sieve having a mesh size from about 10 microns toabout 25 microns.

In some embodiments, the method of extracting a diatom frustule portioncan comprise sorting the plurality of diatom frustule portions toseparate a first diatom frustule portion from a second diatom frustuleportion, the first diatom frustule portion having a greater longestdimension. For example, the first diatom frustule portion may comprise aplurality of unbroken diatom frustule portions. The second diatomfrustule portion may comprise a plurality of broken diatom frustuleportions.

In some embodiments, sorting the plurality of diatom frustule portionscan comprise filtering the plurality of diatom frustule portions.Filtering may comprise disturbing agglomeration of the plurality ofdiatom frustule portions. In some embodiments, disturbing agglomerationof the plurality of diatom frustule portions can comprise stirring. Insome embodiments, disturbing agglomeration of the plurality of diatomfrustule portions can comprise shaking. In some embodiments, disturbingagglomeration of the plurality of diatom frustule portions can comprisebubbling.

Filtering may include applying a sieve to the plurality of diatomfrustule portions. For example, the sieve may have a mesh size fromabout 5 microns to about 10 microns, including about 7 microns.

In some embodiments, the method of extracting a diatom frustule portioncan include obtaining a washed diatom frustule portion. Obtaining thewashed diatom frustule portion may comprise washing the plurality ofdiatom frustule portions with a cleaning solvent after removing the atleast one of the organic contaminant and the inorganic contaminant. Insome embodiments, obtaining the washed diatom frustule portion cancomprise washing the diatom frustule portion having the at least onecommon characteristic with a cleaning solvent.

The cleaning solvent may be removed. For example, removing the cleaningsolvent may comprise sedimenting the plurality of diatom frustuleportions after removing at least one of the organic contaminant and theinorganic contaminant. For example, removing the cleaning solvent maycomprise sedimenting the plurality of diatom frustule portions havingthe at least one common characteristic. Sedimenting the plurality ofdiatom frustule portions may comprise centrifuging. In some embodiments,centrifuging can comprise applying a centrifuge suitable for large scaleprocessing. In some embodiments, centrifuging can comprise applying atleast one of a disc stack centrifuge, a decanter centrifuge, and atubular bowl centrifuge.

In some embodiments, at least one of the dispersing solvent and thecleaning solvent can comprise water.

In some embodiments, at least one of dispersing the plurality of diatomfrustule portions in the dispersing solvent and dispersing the pluralityof diatom frustule portions in the surfactant can comprise sonicatingthe plurality of diatom frustules.

The surfactant may comprise a cationic surfactant. For example, thecationic surfactant may comprise at least one of a benzalkoniumchloride, a cetrimonium bromide, a lauryl methyl gluceth-10hydroxypropyl dimonium chloride, a benzethonium chloride, a benzethoniumchloride, a bronidox, a dmethyldioctadecylammonium chloride, and atetramethylammonium hydroxide.

The surfactant may comprise a non-ionic surfactant. For example, thenon-ionic surfactant may comprise at least one of a cetyl alcohol, astearyl alcohol, a cetostearyl alcohol, an oleyl alcohol, apolyoxyethylene glycol alkyl ether, an octaethylene glycol monododecylether, a glucoside alkyl ethers, a decyl glucoside, a polyoxyethyleneglycol octylphenol ethers, an octylphenol ethoxylate (Triton X-100™), anonoxynol-9, a glyceryl laurate, a polysorbate, and a poloxamer.

In some embodiments, the method of extracting a diatom frustule portioncan comprise dispersing the plurality of diatom frustules in an additivecomponent. Dispersing the plurality of diatom frustules in an additivecomponent may be before dispersing the plurality of diatom frustules inthe surfactant. Dispersing the plurality of diatom frustules in anadditive component may be after dispersing the plurality of diatomfrustules in the surfactant. Dispersing the plurality of diatomfrustules in an additive component may be at least partiallysimultaneous with dispersing the plurality of diatom frustules in thesurfactant. The additive component may include at least one of apotassium chloride, an ammonium chloride, an ammonium hydroxide, and asodium hydroxide.

In some embodiments, dispersing the plurality of diatom frustuleportions can comprise obtaining a dispersion comprising about 1 weightpercent to about 5 weight percent of the plurality of diatom frustuleportions.

In some embodiments, removing the organic contaminant can compriseheating the plurality of diatom frustule portions in the presence of ableach. The bleach may include at least one of a hydrogen peroxide and anitric acid. Heating the plurality of diatom frustule portions maycomprise heating the plurality of diatom frustule portions in a solutioncomprising an amount of hydrogen peroxide in a range from about 10volume percent to about 20 volume percent. Heating the plurality ofdiatom frustule portions may comprise heating the plurality of diatomfrustule portions for a duration of about 5 minutes to about 15 minutes.

In some embodiments, removing the organic contaminant can compriseannealing the plurality of diatom frustule portions. In someembodiments, removing the inorganic contaminant can comprise combiningthe plurality of diatom frustule portions with at least one of ahydrochloric acid and a sulfuric acid. Combining the plurality of diatomfrustule portions with at least one of a hydrochloric acid and asulfuric acid may include mixing the plurality of diatom frustuleportions in a solution comprising about 15 volume percent to about 25volume percent of hydrochloric acid. For example, the mixing may be fora duration of about 20 minutes to about 40 minutes.

A method of extracting a diatom frustule portion may include dispersinga plurality of diatom frustule portions with a surfactant, thesurfactant reducing an agglomeration of the plurality of diatom frustuleportions.

The method of extracting a diatom frustule portion may includeextracting a plurality of diatom frustule portions having at least onecommon characteristic using a disc stack centrifuge. In someembodiments, the method of extracting a diatom frustule portion cancomprise dispersing a plurality of diatom frustule portions in adispersing solvent. In some embodiments, at least one of an organiccontaminant and an inorganic contaminant may be removed.

In some embodiments, the at least one common characteristic can includeat least one of a dimension, a shape, a material, and a degree ofbrokenness. The dimension may include at least one of a length and adiameter.

In some embodiments, a solid mixture can comprise the plurality ofdiatom frustule portions. The method of extracting a diatom frustuleportion may comprise reducing a particle dimension of the solid mixture.Reducing the particle dimension of the solid mixture may be beforedispersing the plurality of diatom frustule portions in the dispersingsolvent. In some embodiments, reducing the particle dimension cancomprise grinding the solid mixture. Grinding the solid mixture mayinclude applying to the solid mixture at least one of a mortar and apestle, a jar mill, and a rock crusher.

In some embodiments, a component of the solid mixture having a longestcomponent dimension that is greater than a longest frustule portiondimension of the plurality of diatom frustule portions can be extracted.Extracting the component of the solid mixture may comprise sieving thesolid mixture. Sieving the solid mixture may comprise processing thesolid mixture with a sieve having a mesh size from about 15 microns toabout 25 microns. Sieving the solid mixture may comprise processing thesolid mixture with a sieve having a mesh size from about 10 microns toabout 25 microns.

In some embodiments, the method of extracting a diatom frustule portioncan comprise sorting the plurality of diatom frustule portions toseparate a first diatom frustule portion from a second diatom frustuleportion, the first diatom frustule portion having a greater longestdimension. For example, the first diatom frustule portion may comprise aplurality of unbroken diatom frustule portions. The second diatomfrustule portion may comprise a plurality of broken diatom frustuleportions.

In some embodiments, sorting the plurality of diatom frustule portionscan comprise filtering the plurality of diatom frustule portions.Filtering may comprise disturbing agglomeration of the plurality ofdiatom frustule portions. In some embodiments, disturbing agglomerationof the plurality of diatom frustule portions can comprise stirring. Insome embodiments, disturbing agglomeration of the plurality of diatomfrustule portions can comprise shaking. In some embodiments, disturbingagglomeration of the plurality of diatom frustule portions can comprisebubbling.

Filtering may include applying a sieve to the plurality of diatomfrustule portions. For example, the sieve may have a mesh size fromabout 5 microns to about 10 microns, including about 7 microns.

In some embodiments, the method of extracting a diatom frustule portioncan include obtaining a washed diatom frustule portion. Obtaining thewashed diatom frustule portion may comprise washing the plurality ofdiatom frustule portions with a cleaning solvent after removing the atleast one of the organic contaminant and the inorganic contaminant. Insome embodiments, obtaining the washed diatom frustule portion cancomprise washing the diatom frustule portion having the at least onecommon characteristic with a cleaning solvent.

The cleaning solvent may be removed. For example, removing the cleaningsolvent may comprise sedimenting the plurality of diatom frustuleportions after removing at least one of the organic contaminant and theinorganic contaminant. For example, removing the cleaning solvent maycomprise sedimenting the plurality of diatom frustule portions havingthe at least one common characteristic. Sedimenting the plurality ofdiatom frustule portions may comprise centrifuging. In some embodiments,centrifuging can comprise applying a centrifuge suitable for large scaleprocessing. In some embodiments, centrifuging can comprise applying atleast one of a disc stack centrifuge, a decanter centrifuge, and atubular bowl centrifuge.

In some embodiments, at least one of the dispersing solvent and thecleaning solvent can comprise water.

In some embodiments, at least one of dispersing the plurality of diatomfrustule portions in the dispersing solvent and dispersing the pluralityof diatom frustule portions in the surfactant can comprise sonicatingthe plurality of diatom frustules.

The surfactant may comprise a cationic surfactant. For example, thecationic surfactant may comprise at least one of a benzalkoniumchloride, a cetrimonium bromide, a lauryl methyl gluceth-10hydroxypropyl dimonium chloride, a benzethonium chloride, a benzethoniumchloride, a bronidox, a dmethyldioctadecylammonium chloride, and atetramethylammonium hydroxide.

The surfactant may comprise a non-ionic surfactant. For example, thenon-ionic surfactant may comprise at least one of a cetyl alcohol, astearyl alcohol, a cetostearyl alcohol, an oleyl alcohol, apolyoxyethylene glycol alkyl ether, an octaethylene glycol monododecylether, a glucoside alkyl ethers, a decyl glucoside, a polyoxyethyleneglycol octylphenol ethers, an octylphenol ethoxylate (Triton X-100™), anonoxynol-9, a glyceryl laurate, a polysorbate, and a poloxamer.

In some embodiments, the method of extracting a diatom frustule portioncan comprise dispersing the plurality of diatom frustules in an additivecomponent. Dispersing the plurality of diatom frustules in an additivecomponent may be before dispersing the plurality of diatom frustules inthe surfactant. Dispersing the plurality of diatom frustules in anadditive component may be after dispersing the plurality of diatomfrustules in the surfactant. Dispersing the plurality of diatomfrustules in an additive component may be at least partiallysimultaneous with dispersing the plurality of diatom frustules in thesurfactant. The additive component may include at least one of apotassium chloride, an ammonium chloride, an ammonium hydroxide, and asodium hydroxide.

In some embodiments, dispersing the plurality of diatom frustuleportions can comprise obtaining a dispersion comprising about 1 weightpercent to about 5 weight percent of the plurality of diatom frustuleportions.

In some embodiments, removing the organic contaminant can compriseheating the plurality of diatom frustule portions in the presence of ableach. The bleach may include at least one of a hydrogen peroxide and anitric acid. Heating the plurality of diatom frustule portions maycomprise heating the plurality of diatom frustule portions in a solutioncomprising an amount of hydrogen peroxide in a range from about 10volume percent to about 20 volume percent. Heating the plurality ofdiatom frustule portions may comprise heating the plurality of diatomfrustule portions for a duration of about 5 minutes to about 15 minutes.

In some embodiments, removing the organic contaminant can compriseannealing the plurality of diatom frustule portions. In someembodiments, removing the inorganic contaminant can comprise combiningthe plurality of diatom frustule portions with at least one of ahydrochloric acid and a sulfuric acid. Combining the plurality of diatomfrustule portions with at least one of a hydrochloric acid and asulfuric acid may include mixing the plurality of diatom frustuleportions in a solution comprising about 15 volume percent to about 25volume percent of hydrochloric acid. For example, the mixing may be fora duration of about 20 minutes to about 40 minutes.

A method of forming silver nanostructures on a diatom frustule portionmay include forming a silver seed layer on a surface of the diatomfrustule portion. The method may include forming a nanostructure on theseed layer.

In some embodiments, the nanostructures can comprise at least one of acoating, a nanowire, a nanoplate, a dense array of nanoparticles, ananobelt, and a nanodisk. In some embodiments, the nanostructures cancomprise silver.

Forming the silver seed layer may comprise applying a cyclic heatingregimen to a first silver contributing component and the diatom frustuleportion. In some embodiments, applying the cyclic heating regimen cancomprise applying a cyclic microwave power. Applying the cyclicmicrowave power may comprise alternating a microwave power between about100 Watt and 500 Watt. For example, alternating may comprise alternatingthe microwave power every minute. In some embodiments, alternating cancomprise alternating the microwave power for a duration of about 30minutes. In some embodiments, alternating can comprise alternating themicrowave power for a duration of about 20 minutes to about 40 minutes.

In some embodiments, forming the silver seed layer can comprisecombining the diatom frustule portion with a seed layer solution. Theseed layer solution may include the first silver contributing componentand a seed layer reducing agent. For example, the seed layer reducingagent may be a seed layer solvent. In some embodiments, the seed layerreducing agent and the seed layer solvent can comprise a polyethyleneglycol.

In some embodiments, the seed layer solution can comprise the firstsilver contributing component, a seed layer reducing agent and a seedlayer solvent.

Forming the silver seed layer may comprise mixing the diatom frustuleportion with the seed layer solution. In some embodiments, the mixingcan comprise ultrasonicating.

In some embodiments, the seed layer reducing agent can comprise aN,N-Dimethylformamide, the first silver contributing component cancomprise a silver nitrate, and the seed layer solvent can comprise atleast one of a water and a polyvinylpyrrolidone.

Forming the nanostructure may comprise combining the diatom frustuleportion with a nanostructure forming reducing agent. In someembodiments, forming the nanostructure further may include heating thediatom frustule portion after combining the diatom frustule portion withthe nanostructure forming reducing agent. For example, the heating maycomprise heating to a temperature of about 120° C. to about 160° C.

In some embodiments, forming the nanostructure can include titrating thediatom frustule portion with a titration solution comprising ananostructure forming solvent and a second silver contributingcomponent. In some embodiments, forming the nanostructure can comprisemixing after titrating the diatom frustule portion with the titrationsolution.

In some embodiments, at least one of the seed layer reducing agent andthe nanostructure forming reducing agent can comprise at least one of ahydrazine, a formaldehyde, a glucose, sodium tartrate, an oxalic acid, aformic acid, an ascorbic acid, and an ethylene glycol.

In some embodiments, at least one of the first silver contributingcomponent and the second silver contributing component can comprise atleast one of a silver salt and a silver oxide. For example, the silversalt may include at least one of a silver nitrate and an ammoniacalsilver nitrate, a silver chloride (AgCl), a silver cyanide (AgCN), asilver tetrafluoroborate, a silver hexafluorophosphate, and a silverethylsulphate.

Forming the nanostructure may be in an ambient to reduce oxideformation. For example, the ambient may comprise an argon atmosphere.

In some embodiments, at least one of the seed layer solvent and thenanostructure forming solvent can comprise at least one of a proplyeneglycol, a water, a methanol, an ethanol, a 1-propanol, a 2-propanol a1-methoxy-2-propanol, a 1-butanol, a 2-butanol a 1-pentanol, a2-pentanol, a 3-pentanol, a 1-hexanol, a 2-hexanol, a 3-hexanol, anoctanol, a 1-octanol, a 2-octanol, a 3-octanol, a tetrahydrofurfurylalcohol (THFA), a cyclohexanol, a cyclopentanol, a terpineol, a butyllactone; a methyl ethyl ether, a diethyl ether, an ethyl propyl ether, apolyethers, a diketones, a cyclohexanone, a cyclopentanone, acycloheptanone, a cyclooctanone, an acetone, a benzophenone, anacetylacetone, an acetophenone, a cyclopropanone, an isophorone, amethyl ethyl ketone, an ethyl acetate, a dimethyl adipate, a proplyeneglycol monomethyl ether acetate, a dimethyl glutarate, a dimethylsuccinate, a glycerin acetate, a carboxylates, a propylene carbonate, aglycerin, a diol, a triol, a tetraol, a pentaol, an ethylene glycol, adiethylene glycol, a polyethylene glycol, a propylene glycol, adipropylene glycol, a glycol ether, a glycol ether acetate, a1,4-butanediol, a 1,2-butanediol, a 2,3-butanediol, a 1,3-propanediol, a1,4-butanediol, a 1,5-pentanediol, a 1,8-octanediol, a 1,2-propanediol,a 1,3-butanediol, a 1,2-pentanediol, an etohexadiol, ap-menthane-3,8-diol, a 2-methyl-2,4-pentanediol, a tetramethyl urea, an-methylpyrrolidone, an acetonitrile, a tetrahydrofuran (THF), adimethyl formamide (DMF), a N-methyl formamide (NMF), a dimethylsulfoxide (DMSO), a thionyl chloride and a sulfuryl chloride.

The diatom frustule portion may comprise a broken diatom frustuleportion. The diatom frustule portion may comprise an unbroken diatomfrustule portion. In some embodiments, the diatom frustule portion canbe obtained through a diatom frustule portion separation process. Forexample, the process may comprise at least one of using a surfactant toreduce an agglomeration of a plurality of diatom frustule portions andusing a disc stack centrifuge.

A method of forming zinc-oxide nanostructures on a diatom frustuleportion may include forming a zinc-oxide seed layer on a surface of thediatom frustule portion. The method may comprise forming a nanostructureon the zinc-oxide seed layer.

In some embodiments, the nanostructure can comprise at least one of ananowire, a nanoplate, a dense array of nanoparticles, a nanobelt, and ananodisk. In some embodiments, the nanostructures can comprisezinc-oxide.

Forming the zinc-oxide seed layer may comprise heating a first zinccontributing component and the diatom frustule portion. In someembodiments, heating the first zinc contributing component and thediatom frustule portion can comprise heating to a temperature in a rangefrom about 175° C. to about 225° C.

In some embodiments, forming the nanostructure can comprise applying aheating regimen to the diatom frustule portion having the zinc-oxideseed layer in the presence of a nanostructure forming solutioncomprising a second zinc contributing component. The heating regimen maycomprise heating to a nanostructure forming temperature. For example,the nanostructure forming temperature may be from about 80° C. to about100° C. In some embodiments, the heating may be for a duration of aboutone to about three hours. In some embodiments, the heating regimen cancomprise applying a cyclic heating routine. For example, the cyclicheating routine may include applying a microwave heating to the diatomfrustule portion having the zinc-oxide seed layer for a heating durationand then turning the microwaving heating off for a cooling duration, fora total cyclic heating duration. In some embodiments, the heatingduration can be about 1 minute to about 5 minutes. In some embodiments,the cooling duration can be about 30 seconds to about 5 minutes. Thetotal cyclic heating duration may be about 5 minutes to about 20minutes. Applying the microwave heating may include applying about 480Watt to about 520 Watt of microwave power, including about 80 Watt toabout 120 Watt of microwave power.

In some embodiments, at least one of the first zinc contributingcomponent and the second zinc contributing component can comprise atleast one of a zinc acetate, a zinc acetate hydrate, a zinc nitrate, azinc nitrate hexahydrate, a zinc chloride, a zinc sulfate, and a sodiumzincate.

In some embodiments, the nanostructure forming solution may include abase. For example, the base may comprise at least one of a sodiumhydroxide, an ammonium hydroxide, potassium hydroxide, ateramethylammonium hydroxide, a lithium hydroxide, ahexamethylenetetramine, an ammonia solution, a sodium carbonate, and aethylenediamine.

In some embodiments, forming the nanostructure can comprise adding anadditive component. The additive component may include at least one of atributylamine, a triethylamine, a triethanolamine, a diisopropylamine,an ammonium phosphate, a 1,6-hexadianol, a triethyldiethylnol, anisopropylamine, a cyclohexylamine, a n-butylamine, an ammonium chloride,a hexamethylenetetramine, an ethylene glycol, an ethanoamine, apolyvinylalcohol, a polyethylene glycol, a sodium dodecyl sulphate, acetyltrimethyl ammonium bromide, and a carbamide.

In some embodiments, at least one of the nanostructure forming solutionand a zinc-oxide seed layer forming solution can comprise a solvent, thesolvent comprising at least one of a proplyene glycol, a water, amethanol, an ethanol, a 1-propanol, a 2-propanol a 1-methoxy-2-propanol,a 1-butanol, a 2-butanol a 1-pentanol, a 2-pentanol, a 3-pentanol, a1-hexanol, a 2-hexanol, a 3-hexanol, an octanol, a 1-octanol, a2-octanol, a 3-octanol, a tetrahydrofurfuryl alcohol (THFA), acyclohexanol, a cyclopentanol, a terpineol, a butyl lactone; a methylethyl ether, a diethyl ether, an ethyl propyl ether, a polyethers, adiketones, a cyclohexanone, a cyclopentanone, a cycloheptanone, acyclooctanone, an acetone, a benzophenone, an acetylacetone, anacetophenone, a cyclopropanone, an isophorone, a methyl ethyl ketone, anethyl acetate, a dimethyl adipate, a proplyene glycol monomethyl etheracetate, a dimethyl glutarate, a dimethyl succinate, a glycerin acetate,a carboxylates, a propylene carbonate, a glycerin, a diol, a triol, atetraol, a pentaol, an ethylene glycol, a diethylene glycol, apolyethylene glycol, a propylene glycol, a dipropylene glycol, a glycolether, a glycol ether acetate, a 1,4-butanediol, a 1,2-butanediol, a2,3-butanediol, a 1,3-propanediol, a 1,4-butanediol, a 1,5-pentanediol,a 1,8-octanediol, a 1,2-propanediol, a 1,3-butanediol, a1,2-pentanediol, an etohexadiol, a p-menthane-3,8-diol, a2-methyl-2,4-pentanediol, a tetramethyl urea, a n-methylpyrrolidone, anacetonitrile, a tetrahydrofuran (THF), a dimethyl formamide (DMF), aN-methyl formamide (NMF), a dimethyl sulfoxide (DMSO), a thionylchloride and a sulfuryl chloride.

The diatom frustule portion may comprise a broken diatom frustuleportion. The diatom frustule portion may comprise an unbroken diatomfrustule portion. In some embodiments, the diatom frustule portion canbe obtained through a diatom frustule portion separation process. Forexample, the process may comprise at least one of using a surfactant toreduce an agglomeration of a plurality of diatom frustule portions andusing a disc stack centrifuge.

A method of forming carbon nanostructures on a diatom frustule portionmay include forming a metal seed layer on a surface of the diatomfrustule portion. The method may include forming a carbon nanostructureon the seed layer.

In some embodiments, the carbon nanostructure can comprise a carbonnanotube. The carbon nanotube may comprise at least one of asingle-walled carbon nanotube and a multi-walled carbon nanotube.

In some embodiments, forming the metal seed layer can comprise spraycoating the surface of the diatom frustule portion. In some embodiments,forming the metal seed layer can comprise introducing the surface of thediatom frustule portion to at least one of a liquid comprising themetal, a gas comprising the metal and the solid comprising a metal.

In some embodiments, forming the carbon nanostructure can comprise usingchemical vapor deposition (CVD). Forming the carbon nanostructure cancomprise exposing the diatom frustule portion to a nanostructure formingreducing gas after exposing the diatom frustule portion to ananostructure forming carbon gas. Forming the carbon nanostructure maycomprise exposing the diatom frustule portion to a nanostructure formingreducing gas before exposing the diatom frustule portion to ananostructure forming carbon gas. In some embodiments, forming thecarbon nanostructure comprises exposing the diatom frustule portion to ananostructure forming gas mixture comprising a nanostructure formingreducing gas and a nanostructure forming carbon gas. The nanostructureforming gas mixture may include a neutral gas. For example, the neutralgas may be argon.

In some embodiments, the metal can comprise at least one of a nickel, aniron, a cobalt, a cobalt-molibdenium bimetallic, a copper, a gold, asilver, a platinum, a palladium, a manganese, an aluminum, a magnesium,a chromium, an antimony, an aluminum-iron-molybdenum (Al/Fe/Mo), an ironpentacarbonyl (Fe(CO)₅)), an iron (III) nitrate hexahydrate((Fe(NO₃)₃.6H₂O), a colbalt (II) chloride hexahydrate (CoCl₂.6H₂O), anammonium molybdate tetrahydrate ((NH₄)₆Mo₇O₂₄·4H₂O), a molybdenum (VI)dichloride dioxide MoO₂Cl₂, and an alumina nanopowder.

In some embodiments, the nanostructure forming reducing gas can compriseat least one of an ammonia, a nitrogen, and a hydrogen. Thenanostructure forming carbon gas may comprise at least one of anacetylene, an ethylene, an ethanol, a methane, a carbon oxide, and abenzene.

In some embodiments, forming the metal seed layer can comprise forming asilver seed layer. Forming the silver seed layer may comprise forming asilver nanostructure on the surface of the diatom frustule portion.

The diatom frustule portion may comprise a broken diatom frustuleportion. The diatom frustule portion may comprise an unbroken diatomfrustule portion. In some embodiments, the diatom frustule portion canbe obtained through a diatom frustule portion separation process. Forexample, the process may comprise at least one of using a surfactant toreduce an agglomeration of a plurality of diatom frustule portions andusing a disc stack centrifuge.

A method of fabricating a silver ink may include combining anultraviolet light sensitive component and a plurality of diatom frustuleportions having a silver nanostructure on a surface of the plurality ofdiatom frustule portions, the surface comprising a plurality ofperforations.

In some embodiments, the method of fabricating the silver ink cancomprise forming a silver seed layer on the surface of the plurality ofdiatom frustule portions. In some embodiments, the method can includeforming the silver nanostructure on the seed layer.

The plurality of diatom frustule portions may include a plurality ofbroken diatom frustule portions. The plurality of diatom frustuleportions may include a plurality of diatom frustule flakes.

In some embodiments, the silver ink is depositable in a layer having athickness of about 5 microns to about 15 microns after curing. In someembodiments, at least one of the plurality of perforations has adiameter of about 250 nanometers to about 350 nanometers. In someembodiments, the silver nanostructure can comprise a thickness of about10 nanometers to about 500 nanometers. The silver ink may comprise anamount of diatom frustules within a range of about 50 weight percent toabout 80 weight percent.

Forming the silver seed layer may include forming the silver seed layeron a surface within the plurality of perforations to form a plurality ofsilver seed plated perforations. Forming the silver seed layer mayinclude forming the silver seed layer on substantially all surfaces ofthe plurality of diatom frustule portions.

In some embodiments, forming the silver nanostructure may compriseforming the silver nanostructure on a surface within the plurality ofperforations to form a plurality of silver nanostructure platedperforations. Forming the silver nanostructure may comprise forming thesilver nanostructure on substantially all surfaces of the plurality ofdiatom frustule portions.

In some embodiments, the ultraviolet light sensitive component can besensitive to an optical radiation having a wavelength shorter than adimension of the plurality of perforations. The ultraviolet lightsensitive component may be sensitive to an optical radiation having awavelength shorter than a dimension of at least one of the plurality ofsilver seed plated perforations and the plurality of silvernanostructure plated perforations.

In some embodiments, combining the plurality of diatom frustule portionswith the ultraviolet light sensitive component can include combining theplurality of diatom frustule portions with a photoinitiation synergistagent. For example, the photoinitiation synergist agent may comprise atleast one of an ethoxylated hexanediol acrylate, a propoxylatedhexanediol acrylate, an ethoxylated trimethylpropane triacrylate, atriallyl cyanurate and an acrylated amine.

In some embodiments, combining the plurality of diatom frustule portionswith the ultraviolet light sensitive component can include combining theplurality of diatom frustule portions with a photoinitiator agent. Thephotoinitiator agent may include at least one of a2-methyl-1-(4-methylthio)phenyl-2-morpholinyl-1-propanon and anisopropyl thioxothanone.

In some embodiments, combining the plurality of diatom frustule portionswith the ultraviolet light sensitive component can include combining theplurality of diatom frustule portions with a polar vinyl monomer. Forexample, the polar vinyl monomer may include at least one of an-vinyl-pyrrolidone and a n-vinylcaprolactam.

The method of fabricating the silver ink may comprise combining theplurality of diatom frustule portions with a rheology modifying agent.In some embodiments, the method of fabricating the silver ink cancomprise combining the plurality of diatom frustule portions with acrosslinking agent. In some embodiments, the method can includecombining the plurality of diatom frustule portions with a flow andlevel agent. In some embodiments, the method can include combining theplurality of diatom frustule portions with at least one of an adhesionpromoting agent, a wetting agent, and a viscosity reducing agent.

The silver nanostructure may include at least one of a coating, ananowire, a nanoplate, a dense array of nanoparticles, a nanobelt, and ananodisk.

In some embodiments, forming the silver seed layer can comprise applyinga cyclic heating regimen to a first silver contributing component andthe plurality of diatom frustule portions.

Forming the silver seed layer may comprise combining the diatom frustuleportion with a seed layer solution. For example, the seed layer solutionmay comprise the first silver contributing component and a seed layerreducing agent.

Forming the silver nanostructure may comprise combining the diatomfrustule portion with a nanostructure forming reducing agent. In someembodiments, forming the silver nanostructure can comprise heating thediatom frustule portion after combining the diatom frustule portion withthe nanostructure forming reducing agent. In some embodiments, formingthe silver nanostructure can comprise titrating the diatom frustuleportion with a titration solution comprising a nano structure formingsolvent and a second silver contributing component.

In some embodiments, the plurality of diatom frustule portions can beobtained through a diatom frustule portion separation process. Forexample, the process may include at least one of using a surfactant toreduce an agglomeration of a plurality of diatom frustule portions andusing a disc stack centrifuge.

A conductive silver ink may include an ultraviolet light sensitivecomponent. The conductive ink may include a plurality of diatom frustuleportions having a silver nanostructure on a surface of the plurality ofdiatom frustule portions, the surface comprising a plurality ofperforations.

The plurality of diatom frustule portions may include a plurality ofbroken diatom frustule portions. The plurality of diatom frustuleportions may include a plurality of diatom frustule flakes.

In some embodiments, the silver ink is depositable in a layer having athickness of about 5 microns to about 15 microns (e.g., after curing).In some embodiments, at least one of the plurality of perforations has adiameter of about 250 nanometers to about 350 nanometers. In someembodiments, the silver nanostructure can comprise a thickness of about10 nanometers to about 500 nanometers. The silver ink may comprise anamount of diatom frustules within a range of about 50 weight percent toabout 80 weight percent.

In some embodiments, at least one of the plurality of perforations cancomprise a surface having a silver nanostructure.

In some embodiments, at least one of the plurality of perforationscomprises a surface having a silver seed layer. In some embodiments,substantially all surfaces of the plurality of diatom frustule portionscan comprise a silver nanostructure.

In some embodiments, the ultraviolet light sensitive component can besensitive to an optical radiation having a wavelength shorter than adimension of the plurality of perforations.

In some embodiments, the conductive silver ink can be curable by anultraviolet radiation. In some embodiments, the plurality ofperforations can have a dimension sufficient to allow the ultravioletradiation to pass through. The conductive silver ink may be depositablein a layer having a thickness of about 5 microns to about 15 microns(e.g., after curing).

In some embodiments, the conductive silver ink can be thermally curable.

The ultraviolet light sensitive component may include a photoinitiationsynergist agent. For example, the photoinitiation synergist agent maycomprise at least one of an ethoxylated hexanediol acrylate, apropoxylated hexanediol acrylate, an ethoxylated trimethylpropanetriacrylate, a triallyl cyanurate and an acrylated amine.

The ultraviolet light sensitive component may include a photoinitiatoragent. The photoinitiator agent may include at least one of a2-methyl-1-(4-methylthio)phenyl-2-morpholinyl-1-propanon and anisopropyl thioxothanone.

In some embodiments, the ultraviolet light sensitive component caninclude a polar vinyl monomer. For example, the polar vinyl monomer mayinclude at least one of a n-vinyl-pyrrolidone and a n-vinylcaprolactam.

The conductive silver ink may include at least one of a rheologymodifying agent, a crosslinking agent, a flow and level agent, aadhesion promoting agent, a wetting agent, and a viscosity reducingagent. In some embodiments, the silver nanostructure can comprise atleast one of a coating, a nanowire, a nanoplate, a dense array ofnanoparticles, a nanobelt, and a nanodisk.

A method of fabricating a silver film may include curing a mixturecomprising an ultraviolet light sensitive component and a plurality ofdiatom frustule portions having a silver nanostructure on a surface ofthe plurality of diatom frustule portions, the surface comprising aplurality of perforations.

In some embodiments, the method of fabricating the silver film cancomprise forming a silver seed layer on the surface of the plurality ofdiatom frustule portions. In some embodiments, the method can compriseforming the silver nanostructure on the seed layer. In some embodiments,the method can include combining the plurality of diatom frustuleportions with the ultraviolet light sensitive component to form a silverink.

The plurality of diatom frustule portions may comprise a plurality ofbroken diatom frustule portions. The plurality of diatom frustuleportions may comprise a plurality of diatom frustule flakes.

In some embodiments, the silver ink is depositable in a layer having athickness of about 5 microns to about 15 microns (e.g., after curing).In some embodiments, at least one of the plurality of perforations has adiameter of about 250 nanometers to about 350 nanometers. In someembodiments, the silver nanostructure can comprise a thickness of about10 nanometers to about 500 nanometers. The silver ink may comprise anamount of diatom frustules within a range of about 50 weight percent toabout 80 weight percent.

Forming the silver seed layer may comprise forming the silver seed layeron a surface within the plurality of perforations to form a plurality ofsilver seed plated perforations. Forming the silver seed layer maycomprise forming the silver seed layer on substantially all surfaces ofthe plurality of diatom frustule portions.

Forming the silver nanostructure may comprise forming the silvernanostructure on a surface within the plurality of perforations to forma plurality of silver nanostructure plated perforations. Forming thesilver nanostructure may comprise forming the silver nanostructure onsubstantially all surfaces of the plurality of diatom frustule portions.

In some embodiments, curing the mixture can comprise exposing themixture to an ultraviolet light having a wavelength shorter than adimension of the plurality of perforations. In some embodiments, curingthe mixture can comprise exposing the mixture to an ultraviolet lighthaving a wavelength shorter than a dimension of at least one of theplurality of silver seed plated perforations and the plurality of silvernanostructure plated perforations.

In some embodiments, curing the mixture can comprise thermally curingthe mixture.

The ultraviolet light sensitive component may be sensitive to an opticalradiation having a wavelength shorter than a dimension of the pluralityof perforations. In some embodiments, the ultraviolet light sensitivecomponent can be sensitive to an optical radiation having a wavelengthshorter than a dimension of at least one of the plurality of silver seedplated perforations and the plurality of silver nanostructure platedperforations.

Combining the plurality of diatom frustule portions with the ultravioletlight sensitive component may comprise combining the plurality of diatomfrustule portions with a photoinitiation synergist agent. For example,the photoinitiation synergist agent may include at least one of anethoxylated hexanediol acrylate, a propoxylated hexanediol acrylate, anethoxylated trimethylpropane triacrylate, a triallyl cyanurate and anacrylated amine.

In some embodiments, combining the plurality of diatom frustule portionswith the ultraviolet light sensitive component can comprise combiningthe plurality of diatom frustule portions with a photoinitiator agent.The photoinitiator agent may include at least one of a2-methyl-1-(4-methylthio)phenyl-2-morpholinyl-1-propanon and anisopropyl thioxothanone.

In some embodiments, combining the plurality of diatom frustule portionswith the ultraviolet light sensitive component can comprise combiningthe plurality of diatom frustule portions with a polar vinyl monomer.The polar vinyl monomer may include at least one of an-vinyl-pyrrolidone and a n-vinylcaprolactam.

The method of fabricating the conductive silver ink may includecombining the plurality of diatom frustule portions with a rheologymodifying agent. In some embodiments, the method of fabricating theconductive silver ink can include combining the plurality of diatomfrustule portions with a crosslinking agent. In some embodiments, themethod can comprise combining the plurality of diatom frustule portionswith a flow and level agent. The method may include combining theplurality of diatom frustule portions with at least one of an adhesionpromoting agent, a wetting agent, and a viscosity reducing agent.

In some embodiments, the silver nanostructure can comprise at least oneof a coating, a nanowire, a nanoplate, a dense array of nanoparticles, ananobelt, and a nanodisk.

In some embodiments, forming the silver seed layer can comprise applyinga cyclic heating regimen to a first silver contributing component andthe plurality of diatom frustule portions.

Forming the silver seed layer may comprise combining the diatom frustuleportion with a seed layer solution. For example, the seed layer solutionmay comprise the first silver contributing component and a seed layerreducing agent.

Forming the silver nanostructure may comprise combining the diatomfrustule portion with a nanostructure forming reducing agent. In someembodiments, forming the silver nanostructure can comprise heating thediatom frustule portion after combining the diatom frustule portion withthe nanostructure forming reducing agent. In some embodiments, formingthe silver nanostructure can comprise titrating the diatom frustuleportion with a titration solution comprising a nanostructure formingsolvent and a second silver contributing component.

In some embodiments, the plurality of diatom frustule portions can beobtained through a diatom frustule portion separation process. Forexample, the process may include at least one of using a surfactant toreduce an agglomeration of a plurality of diatom frustule portions andusing a disc stack centrifuge.

A conductive silver film may include a plurality of diatom frustuleportions having a silver nanostructure on a surface of each of theplurality of diatom frustule portions, the surface comprising aplurality of perforations.

In some embodiments, the plurality of diatom frustule portions cancomprise a plurality of broken diatom frustule portion. The plurality ofdiatom frustule portions may include a plurality of diatom frustuleflakes.

In some embodiments, at least one of the plurality of perforations has adiameter of about 250 nanometers to about 350 nanometers. In someembodiments, the silver nanostructure can comprise a thickness of about10 nanometers to about 500 nanometers.

In some embodiments, at least one of the plurality of perforations cancomprise a surface having a silver nanostructure. In some embodiments,at least one of the plurality of perforations can comprise a surfacehaving a silver seed layer. Substantially all surfaces of the pluralityof diatom frustule portions may comprise a silver nanostructure.

In some embodiments, the silver nanostructure can comprise at least oneof a coating, a nanowire, a nanoplate, a dense array of nanoparticles, ananobelt, and a nanodisk.

In some embodiments, the conductive silver film can comprise a binderresin.

For purposes of summarizing the invention and the advantages achievedover the prior art, certain objects and advantages are described herein.Of course, it is to be understood that not necessarily all such objectsor advantages need to be achieved in accordance with any particularembodiment. Thus, for example, those skilled in the art will recognizethat the invention may be embodied or carried out in a manner that canachieve or optimize one advantage or a group of advantages withoutnecessarily achieving other objects or advantages.

All of these embodiments are intended to be within the scope of theinvention herein disclosed. These and other embodiments will becomereadily apparent to those skilled in the art from the following detaileddescription having reference to the attached figures, the invention notbeing limited to any particular disclosed embodiment(s).

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the presentdisclosure are described with reference to the drawings of certainembodiments, which are intended to illustrate certain embodiments andnot to limit the invention.

FIG. 1 is a scanning electron microscope (SEM) image of diatomaceousearth comprising frustules.

FIG. 2 is a SEM image of an example frustule including a porous surface.

FIG. 3 is a SEM image of example frustules each having a substantiallycylindrical shape.

FIGS. 4A and 4B are a flow diagram of example steps of a frustuleseparation process.

FIG. 5A shows an example embodiment of a frustule comprising structureson both an exterior surface and an interior surface.

FIG. 5B shows a SEM image, at 50 k× magnification, of an examplefrustule surface seeded with silver.

FIG. 5C shows a SEM image, at 250 k× magnification, of a frustulesurface seeded with silver.

FIG. 5D shows a SEM image, at 20 k× magnification, of a frustule surfacehaving silver nanostructures formed thereon.

FIG. 5E shows a SEM image, at 150 k× magnification of a frustule surfacehaving silver nanostructures formed thereon.

FIG. 5F shows a SEM image, at 25 k× magnification, of a diatom frustuleflake having a surface coated by silver nanostructures.

FIG. 5G shows a SEM image, at 100 k× magnification, of a frustulesurface seeded with zinc-oxide.

FIG. 5H shows a SEM image, at 100 k× magnification, of a frustulesurface seeded with zinc-oxide.

FIG. 5I shows a SEM image, at 50 k× magnification, of a frustule surfacehaving zinc-oxide nanowires formed thereon.

FIG. 5J shows a SEM image, at 25 k× magnification, of a frustule surfacehaving zinc-oxide nanowires formed thereon.

FIG. 5K shows a SEM image, at 10 k× magnification, of a frustule surfacehaving zinc-oxide nanoplates formed thereon.

FIG. 6 schematically illustrates an example embodiment of an energystorage device.

FIG. 7 shows an example embodiment of a separator for an energy storagedevice incorporating frustules in a separator layer.

FIG. 8 shows an example embodiment of an electrode for an energy storagedevice incorporating frustules in an electrode layer.

DETAILED DESCRIPTION

Although certain embodiments and examples are described below, those ofskill in the art will appreciate that the invention extends beyond thespecifically disclosed embodiments and/or uses and obvious modificationsand equivalents thereof. Thus, it is intended that the scope of theinvention herein disclosed should not be limited by any particularembodiments described below.

Energy storage devices used to power electronic devices generallyinclude batteries (e.g., rechargeable batteries), capacitors, andsuper-capacitors (e.g., EDLC). Energy storage devices may comprise anasymmetric energy storage device, including, for example, abattery-capacitor hybrid. Energy storage devices can be manufacturedusing printing technologies such as screen printing, roll-to-rollprinting, ink-jet printing, etc. Printed energy storage devices canfacilitate reduced energy storage device thickness, enabling compactenergy storage. Printed energy storage devices can enable increasedenergy storage density by facilitating, for example, stacking of theenergy storage devices. Increased energy storage density may facilitateuse of printed energy storage devices for applications having a largepower requirement, such as solar energy storage. Unlike energy storagedevices having a rigid outer casing, printed energy storage devices maybe implemented on a flexible substrate, enabling a flexible energystorage device. A flexible energy storage device can facilitatefabrication of flexible electronic devices, such as flexible electronicdisplay media. Due to reduced thickness and/or flexible structure,printed energy storage devices may power cosmetic patches, medicaldiagnostic products, remote sensor arrays, smartcards, smart packaging,smart clothing, greeting cards, etc.

Reliability and durability of a printed energy storage device may be afactor hindering increased adoption of printed batteries. Printed energystorage devices typically lack a rigid outer casing, so printed energystorage devices may not stand up well to compressive pressure or shapedeforming manipulation in use or production. Variation of an energystorage device layer thickness in response to compressive pressure orshape deforming manipulation may adversely affect device reliability.For example, some printed energy storage devices include electrodesspaced by a separator. Deviations in separator thickness may cause ashort between the electrodes, such as when a separator is compressibleand fails to maintain a separation between the electrodes undercompressive pressure or shape deforming manipulation.

Costs associated with fabricating a printed energy storage device mayalso be a factor hampering use of printed energy storage devices topower a wider range of applications. Reliable fabrication of energystorage devices using printing technologies may facilitatecost-effective energy storage device production. Printing of an energystorage device may enable integrating the device printing process intothe production of electronic devices, including for example printedelectronic devices powered by the printed energy storage device,possibly enabling further cost savings. However, inadequate devicestructural robustness may hinder device integrity throughout thefabrication process, decreasing the feasibility of some printingtechnologies and impeding cost-effective production of the printedenergy storage devices. Thickness of a printed energy storage devicelayer may also impede the use of certain printing technologies in thefabrication process, for example due to a device layer thickness that isgreater than a film thickness at which the printing technology caneffectively print.

As described herein, frustules may have significant mechanical strengthor resistance to shear stress, for example due to dimensions, shape,porosity, and/or material. According to some implementations describedherein, an energy storage device includes one or more components, forexample one or more layers or membranes of a printed energy storagedevice, comprising frustules. An energy storage device comprisingfrustules may have mechanical strength and/or structural integrity suchthat the energy storage device is able to withstand compressive pressureand/or shape deforming manipulation, which can occur during manufactureor use, without failure, such that device reliability can increase. Anenergy storage device comprising frustules can resist variations inlayer thicknesses, enabling maintenance of uniform or substantiallyuniform device layer thicknesses. For example, a separator comprisingfrustules may withstand compressive pressure or shape deformingmanipulation to thereby facilitate improved energy storage devicereliability by maintaining a uniform or substantially uniform separationdistance between electrodes to inhibit or prevent a short in the device.

Increased mechanical strength in energy storage devices comprisingfrustules may facilitate reliable fabrication of the energy storagedevices using various printing technologies, thereby enablingcost-effective device fabrication due to increased yield and/orintegration of the fabrication process with the production process ofapplications powered by the devices.

Energy storage devices may be printed using an ink comprising frustules.For example, one or more membranes of a printed energy storage devicemay comprise frustules. One or more membranes of a printed energystorage device having frustules may be reliably printed onto a varietyof substrates, including but not limited to, a flexible or inflexiblesubstrate, a textile, a device, a plastic, any variety of films such asa metallic or semiconductor film, any variety of paper, combinationsthereof, and/or the like. For example, suitable substrates may includegraphite paper, graphene paper, polyester film (e.g., Mylar),polycarbonate film aluminum foil, copper foil, stainless steel foil,carbon foam, combinations thereof, and/or the like. Fabrication ofprinted energy storage devices on flexible substrates may allow forflexible printed energy storage devices that can be used in a wide arrayof devices and implementations due to increased reliability of certainsuch printed energy storage devices, for example due to increasedrobustness as a result of one or more layers comprising frustules.

Improved mechanical strength in printed energy storage devicescomprising frustules may also enable a reduced printed device layerthickness. For example, frustules may provide structural support for anenergy storage device layer, enabling thinner layers having sufficientstructural robustness to withstand compressive pressure or shapedeforming manipulation, which can then reduce an overall devicethickness. Decreased thickness of printed energy storage devices canfurther facilitate energy storage density of the printed devices and/orenable wider use of the printed devices.

A printed energy storage device comprising frustules may have improveddevice performance, for example improved device efficiency. Reducedthickness of an energy storage device layer may enable improved deviceperformance. Performance of an energy storage device may depend at leastin part on the internal resistance of the energy storage device. Forexample, performance of an energy storage device may depend at least inpart on a separation distance between a first and a second electrode. Adecreased separator membrane thickness for a given measure ofreliability reduces a distance between a first and a second electrode,which can reduce the internal resistance and improve an efficiency ofthe energy storage device. Internal resistance of an energy storagedevice may also depend at least in part on the mobility of ionic speciesbetween a first and a second electrode. Porosity of frustule surfacesmay enable mobility of ionic species. For example, a separatorcomprising frustules may enable a more structurally robust separationbetween electrodes of an energy storage device while facilitatingmobility of ionic species between the electrodes. Frustule surfaceporosity may facilitate a direct path for mobile ionic species between afirst electrode and a second electrode, reducing a resistance and/orincreasing efficiency. Reduced thickness of an electrode layercomprising frustules and porosity of the electrode frustules may alsoenable improved storage device performance. A reduced electrodethickness may provide increased access of ionic species to activematerials within the electrode. Porosity and/or conductivity offrustules in an electrode may facilitate mobility of the ionic specieswithin the electrode. Frustules in an electrode may also enable improveddevice performance by, for example, serving as a substrate on whichactive materials and/or structures comprising active materials may beapplied or formed, enabling increased surface area for active materialsand thereby facilitating access of ionic species to the activematerials.

FIG. 1 is a SEM image of diatomaceous earth comprising frustules 10. Thefrustules 10 have a generally cylindrical shape, although some frustulesare broken or differently shaped. In some embodiments, the cylindricalfrustules 10 have a diameter between about 3 μm and about 5 μm. In someembodiments, the cylindrical frustules 10 have a length between about 10μm and about 20 μm. Other diameters and/or lengths are also possible.The frustules 10 may have significant mechanical strength or resistanceto shear stress, for example due to architecture (e.g., dimensions,shape), material, combinations thereof, and/or the like. For example,mechanical strength of a frustule 10 may be inversely related to thesize of the frustule 10. In some embodiments, a frustule 10 having alongest axis in a range of from about 30 μm to about 130 μm canwithstand compressive forces from about 90 μN to about 730 μN.

FIG. 2 is a SEM image of an example frustule 10 including a poroussurface 12. The porous surface 12 includes circular or substantiallycircular openings 14. Other shapes of the openings 14 are also possible(e.g., curved, polygonal, elongate, etc.). In some embodiments, theporous surface 12 of a frustule 10 has a uniform or substantiallyuniform porosity, for example including openings 14 having uniform orsubstantially uniform shape, dimensions, and/or spacing (e.g., as shownin FIG. 2). In some embodiments, the porous surface 12 of a frustule 10has a varying porosity, for example including openings 14 havingdifferent shapes, dimensions, and/or spacing. The porous surfaces 12 ofa plurality of frustules 10 can have uniform or substantially uniformporosities, or porosity of the porous surfaces 12 of different frustules10 may vary. A porous surface 12 may comprise nanoporosity, includingfor example microporosity, mesoporosity, and/or macroporosity.

FIG. 3 is a SEM image of example frustules 10 each having a cylindricalor substantially cylindrical shape. Frustule features may differ amongdifferent species of diatoms, each diatom species having frustules of adifferent shape, size, porosity, material, and/or another frustuleattribute. Diatomaceous earth, which may be commercially available(e.g., from Mount Sylvia Diatomite Pty Ltd of Canberra, Australia,Continental Chemical USA of Fort Lauderdale, Fla., Lintech InternationalLLC of Macon, Ga., etc.), can serve as a source of frustules. In someembodiments, diatomaceous earth is sorted according to a pre-determinedfrustule feature. For example, sorting may result in frustules eachincluding a predetermined feature, such as shape, dimensions, material,porosity, combinations thereof, and/or the like. Sorting frustules mayinclude one or a variety of separation processes such as, for example,filtering, screening (e.g., use of vibrating sieves for separationaccording to a frustule shape or size), a separation process involvingvoraxial or centrifugal technology (e.g., for separation according tofrustule density), any other suitable solid-solid separation processes,combinations thereof, and/or the like. Frustules may also be available(e.g., from a commercial source) already sorted according to a frustulefeature such that the frustules already comprise a uniform orsubstantially uniform shape, size, material, porosity, anotherpre-determined frustule attribute, combinations thereof, and/or thelike. For example, frustules available from a geographic region (e.g., aregion of a country such as the United States, Peru, Australia, etc.; aregion of the globe; etc.) and/or a type of natural environment (e.g.,freshwater environment, saltwater environment, etc.) may comprisefrustules of a species typically found in that geographic region and/orenvironment, providing frustules having a uniform or substantiallyuniform shape, size, material, porosity, another pre-determined frustuleattribute, combinations thereof, and/or the like.

In some embodiments, a separation process can be used to sort frustulessuch that only or substantially only unbroken frustules are retained. Insome embodiments, the separation process can be used to remove broken orsmall frustules, resulting in only or substantially onlycylindrically-shaped frustules 10 having certain lengths and/ordiameters (e.g., as illustrated in FIG. 3). The separation process toremove broken frustules may include screening, such as with the use of asieve having a mesh size selected to retain only or substantially onlyfrustules having a pre-determined dimension. For example, the mesh sizeof the sieve may be selected to remove frustules having a dimension(e.g., a length or diameter) of no more than about 40 μm, no more thanabout 30 μm, no more than about 20 μm or no more than about 10 μm, andincluding ranges bordering and including the foregoing values. Othersieve mesh sizes may also be suitable.

In some embodiments, the separation process to remove broken frustulesincludes application of ultrasonic waves to frustules placed in a fluiddispersion, including for example ultrasonication during which frustulesdispersed in a water bath are subjected to ultrasonic waves. Sonicationparameters such as power, frequency, duration, and/or the like may beadjusted based at least in part on one or more attributes of thefrustules. In some embodiments, ultrasonication includes use of soundwaves having a frequency between about 20 kilohertz (kHz) and about 100kHz, between about 30 kHz and about 80 kHz, and between about 40 kHz andabout 60 kHz. In some embodiments, ultrasonication may use sound waveshaving a frequency of about 20 kHz, about 25 kHz, about 30 kHz, about 35kHz, about 40 kHz, about 45 kHz, and ranges bordering and including theforegoing values. The ultrasonication step may have a duration betweenabout 2 minutes and about 20 minutes, between about 2 minutes and about15 minutes, and between about 5 minutes and about 10 minutes. In someembodiments, ultrasonication step may have a duration of about 2minutes, about 5 minutes, about 10 minutes, and ranges bordering andincluding the foregoing values. For example, a frustule-fluid sample maybe subjected to ultrasonic waves at a frequency of about 35 kHz for aduration of about 5 minutes.

In some embodiments, separation process includes sedimentation. Forexample, the separation process may include both ultrasonication andsedimentation such that heavier particles from the frustule-fluid samplemay be allowed to settle out from the suspended phase of thefrustule-fluid sample during ultrasonication. In some embodiments, thesedimentation process of heavier particles from the frustule-fluidsample has a duration between about 15 seconds and about 120 seconds,between about 20 seconds and about 80 seconds, and between about 30seconds and about 60 seconds. In some embodiments, sedimentation has aduration of no more than about 120 seconds, no more than about 60seconds, no more than about 45 seconds, no more than or about 30seconds.

The separation process to remove broken frustules may include use ofhigh-velocity centrifugal technology for physical separation based ondensity, including for example an ultracentrifugation step. For example,the separation process may include ultracentrifugation of the suspendedphase of a frustule-fluid sample. Ultracentrifugation parameters such asangular velocity, duration, and/or the like may depend at least in parton the composition of the suspended phase (e.g., a density of thefrustules) and/or characteristics of the equipment used. For example,the suspended phase may be ultracentrifuged at an angular velocitybetween about 10,000 rotations per minute (RPM) and about 40,000 RPM,between about 10,000 RPM and about 30,000 RPM, between about 10,000 RPMand about 20,000 RPM, and between about 10,000 RPM and about 15,000 RPM.The suspended phase may be ultracentrifuged for a duration between about1 minute and about 5 minutes, between about 1 minute and about 3minutes, and between about 1 minute and about 2 minutes. For example,the suspended phase of the frustule-fluid sample may be ultracentrifugedat an angular velocity of about 13,000 RPM for about 1 minute.

FIGS. 4A and 4B are a flow diagram of example steps of a frustuleseparation process 20. The process 20 may enable separation of brokenand/or unbroken diatom frustules from a solid mixture comprising, forexample, broken and unbroken diatom frustules. In some embodiments, theseparation process 20 enables large scale frustule sorting.

As described herein, there can be two sources of diatom frustules fornanostructured materials and/or nanodevices: living diatoms anddiatomaceous earth. Diatoms can be taken directly from nature orcultured. Artificially, a large number of identical silica frustules canbe cultured within a few days. To use natural diatoms for nanostructuredmaterials and/or nanodevices, a separation process can be performed toseparate the diatoms from other organic materials and/or substances.Another approach is to use diatomaceous earth. The sediments areabundant and the material is of low cost.

Diatomaceous earth can have frustules ranging from mixtures of differentdiatom species to a single diatom species (e.g., including somefreshwater sediments). Diatomaceous earth can comprise broken and/orwhole diatom frustules plus contaminating materials of different origin.Depending on application, one may use only whole diatom frustules, onlybroken frustules, or a mixture of both. For example, when separatingwhole frustules, diatomaceous earth with one kind of frustules may beused.

In some embodiments, a method of separating comprises separating wholediatom frustules from broken pieces of diatom frustules. In someembodiments, the separation process comprises sorting whole diatomfrustules according to a common frustule characteristic (e.g., adimension including a length or diameter, a shape, and/or a material)and/or sorting portions of diatom frustules based on a common frustulecharacteristic (e.g., a dimension including a length or diameter, ashape, degree of brokenness, and/or a material). For example, theseparation process may enable extracting a plurality of diatom frustulesor portions of diatom frustules having at least one commoncharacteristic. In some embodiments, the separation process comprisesremoving contaminative material having a different chemical origin fromthe diatom frustules and/or portions of diatom frustules.

Diatoms and diatom frustules that stay unchanged during long timeperiods are sometimes used in biological, ecological, and related earthscience research. Many approaches have been developed to extract smallsamples of frustules from water or sediments. The sediments(diatomaceous earth) contain diatom frustules (broken and unbroken)alongside with carbonates, mica, clay, organics and other sedimentaryparticles. The separation of unbroken frustules may involve three mainsteps: removal of organic remains, removal of particles with differentchemical origin, and removal of broken pieces. The removal of organicmatter may be realized with heating of samples in a bleach (e.g.,hydrogen peroxide and/or nitric acid), and/or annealing at highertemperatures. The carbonates, clay, and other soluble non-silicamaterials may be removed by hydrochloric and/or sulfuric acid. For theseparation of broken and unbroken frustules, several techniques can beapplied: sieving, sedimentation and centrifugation, centrifugation witha heavy liquid, and split-flow lateral-transport thin separation cells,and combinations thereof. A problem for all of these approaches mayoften be aggregation of broken and unbroken frustules, which candiminish the quality of the separation, and/or may render the separationprocess suitable only for laboratory size samples.

Scaling up separation procedures may enable diatom frustules to be usedas industrial nanomaterials.

In some embodiments, a separation procedure that can be utilized forindustrial scale separation of diatoms comprises separation of diatomfrustule portions having at least one common characteristic. Forexample, the common characteristic could be unbroken diatom frustules orbroken diatom frustules. The separation process 20, as shown in FIGS. 4Aand 4B, is an example separation procedure enabling industrial scaleseparation of diatoms. In some embodiments, a separation procedure thatenables large scale separation of diatoms enables a reduction in theagglomeration of frustules, such as by using a surfactant and/or a discstack centrifuge. In some embodiments, use of the surfactant can enablethe large scale separation. In some embodiments, using the disc stackcentrifuge (e.g., a milk separator type centrifugation process) canenable large scale separation. For example, use of the surfactant todisperse diatom frustules together with a disc stack centrifuge to sortfrustules based on a frustule characteristic may facilitate large scaleseparation of diatoms by enabling reduced agglomeration of the diatomfrustules. A traditional, non-disk stack centrifuge process would causesedimentation of the frustules. The supernatant fluid would bediscarded, and the sedimented frustules would be redispersed in asolvent, after which the centrifuge would again cause sedimentation ofthe frustules. This process would be repeated until the desiredseparation is achieved. A disk stack centrifuge process can continuouslyredisperse and separate sedimented frustules. For example, a phaseenriched with whole diatoms can be continuously circulated through thedisk stack centrifuge, becoming more and more enriched. In someembodiments, the disc stack centrifuge can enable a separation of brokendiatom frustules from unbroken diatom frustules. In some embodiments,the disc stack centrifuge can enable a sorting of the diatom frustulesaccording to a diatom frustule characteristic. For example, the discstack centrifuge may enable extraction of frustules having at least onecommon characteristic (e.g., a dimension, a shape, a degree ofbrokenness and/or a material).

A separation procedure enabling industrial scale separation of diatoms,such as the separation process 20 shown in FIGS. 4A and 4B, may includethe following steps:

1. Particles of a solid mixture (e.g., diatomaceous earth) comprisingthe diatom frustules and/or portions of diatom frustules may be rockyand can be broken down into smaller particles. For example, a particlesize of the solid mixture may be reduced to facilitate the separationprocess 20. In some embodiments, to obtain a powder, the diatomaceousearth can be mildly milled or ground, for example using a mortar andpestle, a jar mill, a rock crusher, combinations thereof, and/or thelike.

2. In some embodiments, components of the diatomaceous earth that arelarger than the diatom frustules or portions of diatom frustules may beremoved through a sieving step. In some embodiments, the sieving step isperformed after the diatomaceous earth has been milled. For example,diatomaceous earth powder may be sieved to remove the particles of thepowder which are bigger than the frustules. In some embodiments, thesieving can be facilitated by dispersing the solid mixture (e.g., milleddiatomaceous earth) in a liquid solvent. The solvent may be water,and/or other suitable liquid solvents. Dispersing the solid mixture inthe solvent may be facilitated by sonicating the mixture comprising thesolid mixture and the solvent. Other methods of aiding dispersion mayalso be suitable. In some embodiments, the dispersion comprises a weightpercent of diatoms within a range of from about 1 weight percent toabout 5 weight percent, about 1 weight percent to about 10 weightpercent, about 1 weight percent to about 15 weight percent, or about 1weight percent to about 20 weight percent. A concentration of the solidmixture in the dispersion may be reduced to facilitate the sieving stepto remove particles of the dispersion that are larger than the diatoms.The sieve openings depend on the size of diatoms in the sample. Forexample, a suitable sieve may comprise a mesh size of about 20 microns,or any other mesh size that enables removal from the dispersionparticles of the solid mixture that are larger than the diatoms (e.g., asieve having a mesh size of about 15 microns to about 25 microns, or ofabout 10 microns to about 25 microns). A shaker sieve may be used foreffectively increasing flow through the sieve.

3. In some embodiments, the separation process includes a purificationstep to remove organic contaminants from the diatoms (e.g., diatomfrustules or portions of diatom frustules). A suitable process forremoving organic contaminants may comprise immersing and/or heating thediatoms in a bleach (e.g., nitric acid and/or hydrogen peroxide), and/orannealing the diatoms at higher temperatures. For example, a sample ofdiatoms may be heated in a volume of a solution comprising about 10volume percent to about 50 volume percent (e.g., 30 volume percent)hydrogen peroxide for about 1 minute to about 15 minutes (e.g., 10minutes). Other compositions, concentrations and/or durations may besuitable. For example, the composition of the solution used, theconcentration of the solution used, and/or the duration of the heatingmay depend on the composition of the sample to be purified (e.g., typesof organic contaminants and/or diatoms). In some embodiments, thediatoms can be heated in a solution until the solution ceases orsubstantially ceases to bubble (e.g., indicating removal of organiccontaminants is complete or substantially complete) to facilitatesufficient removal of the organic contaminants. Immersing and/or heatingdiatoms in a solution may be repeated until organic contaminants havebeen removed or substantially removed.

Purification of diatoms from organic contaminants may be followed bywashing with water. In some embodiments, the diatoms may be washed witha liquid solvent (e.g., water). The diatoms may be separated from thesolvent through a sedimentation process, including for example acentrifuge step. Suitable centrifuge technology may include, forexample, a disc stack centrifuge, a decanter centrifuge, a tubular bowlcentrifuge, combinations thereof, and/or the like.

4. In some embodiments, the separation process includes a purificationstep to remove inorganic contaminants. Inorganic contaminants may beremoved by mixing the diatoms with hydrochloric and/or sulfuric acid.Inorganic contaminants may include carbonates, clay, and other solublenon-silica materials. For example, a sample of diatoms may be mixed witha volume of solution comprising about 15 volume percent to about 25volume percent of hydrochloric acid (e.g., about 20 volume percenthydrochloric acid) for a duration of about 20 minutes to about 40minutes (e.g., about 30 minutes). Other compositions, concentrationsand/or durations may be suitable. For example, the composition of thesolution used, the concentration of the solution used, and/or theduration of the mixing may depend on the composition of the sample to bepurified (e.g., types of inorganic contaminants and/or diatoms). In someembodiments, the diatoms can be mixed in a solution until the solutionceases or substantially ceases to bubble (e.g., indicating removal ofinorganic contaminants is complete or substantially complete) tofacilitate sufficient removal of the inorganic contaminants. Mixingdiatoms with a solution may be repeated until inorganic contaminantshave been removed or substantially removed.

Purification of diatoms from soluble inorganic contaminants may befollowed by washing with water. In some embodiments, the diatoms may bewashed with a liquid solvent (e.g., water). The diatoms may be separatedfrom the solvent through a sedimentation process, including for examplea centrifuge step. Suitable centrifuge technology may include, forexample, a disc stack centrifuge, a decanter centrifuge, a tubular bowlcentrifuge, combinations thereof, and/or the like.

5. In some embodiments, the separation process comprises dispersing offrustules in a surfactant. The surfactant may facilitate separation ofthe frustules and/or portions of frustules from one another, reducingagglomeration of the frustules and/or portions of frustules. In someembodiments, an additive is used to reduce agglomeration of the diatoms.For example, diatoms may be dispersed in a surfactant and an additive.In some embodiments, dispersing of the diatoms in the surfactant and/oradditive may be facilitated by sonicating the mixture comprisingdiatoms, the surfactant and/or the additive.

6. In some embodiments, broken frustule pieces may be extracted by a wetsieving process. For example, a filtering process may be used. In someembodiments, the filtering process comprises using a sieve for removingthe smaller pieces of broken frustules. The sieve may comprise a meshsize suitable for removing the smaller pieces of broken frustules (e.g.,a 7 micron sieve). The wet sieving process can inhibit or prevent smallsediment from accumulating in the pores of the sieve and/or allow smallparticles to pass through the pores of the sieve, for example bydisturbing agglomeration of the sediment. Disturbing agglomeration mayinclude, for example, stirring, bubbling, shaking, combinations thereof,and the like of materials which sediment on the sieve mesh. In someembodiments, the filtering process can be continuous through a series ofsieves (e.g., having increasingly smaller pores or mesh sizes) (e.g.,multiple sieves in a machine having a single input and output).

7. In some embodiments, a continuous centrifugation (milk separator—typemachine) of frustules in a liquid can be used. For example, a disc stackcentrifuge may be used. This process may be used to separate the diatomsaccording to a common characteristic, including for example, furtherseparating broken frustule pieces from the unbroken frustules. In someembodiments, disc stack centrifuge step can be repeated to achieve adesired separation (e.g., desired level of separation of the brokenfrustules from the unbroken frustules).

8. As described herein, frustules may be washed in solvent, followed bya sedimentation process (e.g. centrifugation) in order to extract thefrustules from the solvent. For example, centrifugation can be used tosediment frustules or portions of frustules after each washing stepand/or before final use. Suitable centrifuge technology for sedimentingfrustules after a wash step may include continuous centrifuges,including but not limited to a disc stack centrifuge, a decantercentrifuge, and/or a tubular bowl centrifuge.

The example separation procedure has been tested with fresh waterdiatoms from Mount Silvia Pty, Ltd. Diatomite mining company,Queensland, Australia. The majority of frustules in the sample has onekind of diatoms Aulacoseira sp. The frustules have cylindrical shapewith diameter of about 5 microns and length from 10 to 20 microns.

Flow-chart of an example separation procedure, separation process 20presented in FIGS. 4A and 4B only serves as an example. The quantitiesof parameters in the flowchart are provided as illustrative examples(e.g., suited to the chosen sample only). For example, quantities may bedifferent for different types of diatoms.

The surface of diatoms can include amorphous silica and can includesilanol groups, which are negatively charged. Isoelectric point foundfrom zeta potential measurements can often be around pH2 for diatoms(e.g., similar to that of amorphous silica).

In some embodiments, the surfactant can comprise a cationic surfactant.Suitable cationic surfactants can include benzalkonium chloride,cetrimonium bromide, lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride, benzethonium chloride, benzethonium chloride, bronidox,dmethyldioctadecylammonium chloride, tetramethylammonium hydroxide,mixtures thereof, and/or the like. The surfactant may be a nonionicsurfactant. Suitable nonionic surfactants can include: cetyl alcohol,stearyl alcohol, and cetostearyl alcohol, oleyl alcohol, polyoxyethyleneglycol alkyl ethers, octaethylene glycol monododecyl ether, glucosidealkyl ethers, decyl glucoside, polyoxyethylene glycol octylphenolethers, Triton X-100, Nonoxynol-9, glyceryl laurate, polysorbate,poloxamers, mixtures thereof, and/or the like.

In some embodiments, one or more additives can be added to reduceagglomeration. Suitable additives may include: potassium chloride,ammonium chloride, ammonium hydroxide, sodium hydroxide, mixturesthereof, and/or the like.

Frustules may have one or more modifications applied to a surface of thefrustules. In some embodiments, frustules may be used as a substrate toform one or more structures on one or more surfaces of the frustules.FIG. 5A shows an example frustule 50 comprising structures 52. Forexample, a frustule 50 may have a hollow cylindrical or substantiallycylindrical shape, and may comprise structures 52 on both an exteriorand interior surface of the cylinder. The structures 52 may modify oraffect a characteristic or attribute of the frustule 50, including, forexample, the conductivity of the frustule 50. For example, anelectrically insulating frustule 50 may be made electrically conductiveby forming electrically conductive structures 52 on one or more surfacesof the frustule 50. A frustule 50 may include structures 52 comprisingsilver, aluminum, tantalum, brass, copper, lithium, magnesium,combinations thereof, and/or the like. In some embodiments, a frustule50 includes structures 52 comprising ZnO. In some embodiments, afrustule 50 includes structures 52 comprising a semiconductor material,including silicon, germanium, silicon germanium, gallium arsenide,combinations thereof, and/or the like. In some embodiments, frustules 50comprise surface modifying structures 52 on all or substantially all ofthe surfaces of the frustules 50.

Structures 52 applied or formed on a surface of a frustule 50 maycomprise various shapes, dimensions, and/or other attributes. A frustule50 may comprise structures 52 having a uniform or substantially uniformshape, dimension, and/or another structure 52 attribute. In someembodiments, a frustule 50 may have structures 52 comprising nanowires,nanoparticles, structures having a rosette shape, combinations thereof,and/or the like.

Structures 52 can be formed or deposited onto a surface of a frustule 50at least in part by combining a frustule 50 with a formulationcomprising a desired material to allow coating or seeding of thestructures 52 onto a surface of the frustule 50.

As described herein, structures 52 on a surface of the frustule 50 maycomprise zinc oxide, such as zinc oxide nanowires. In some embodiments,zinc oxide nanowires can be formed on a surface of the frustule 50 bycombining the frustule 50 with a solution comprising zinc acetatedihydrate (Zn(CH₃CO₂)₂.2H₂O) and ethanol. For example, a solution havinga concentration of 0.005 mol/L (M) zinc acetate dihydrate in ethanol maybe combined with frustules 50 so as to coat a surface of the frustules50. The coated frustules 50 may then be air dried and rinsed withethanol. In some embodiments, the dried frustules 50 can then beannealed (e.g., at a temperature of about 350° C.). The zinc oxidenanowires may then be allowed to grow on the coated surface of thefrustules 50. In some embodiments, the annealed frustules 50 aremaintained at a temperature above room temperature (e.g., maintained ataround a temperature of about 95° C.) to facilitate formation of thezinc oxide nanowires.

Frustules 50 may also comprise a material formed on or deposited onto asurface of the frustules 50 to modify a characteristic or attribute ofthe frustules 50. For example, an electrically insulating frustule 50may be made electrically conductive by forming or applying anelectrically conductive material on one or more surfaces of the frustule50. A frustule 50 may include a material comprising silver, aluminum,tantalum, brass, copper, lithium, magnesium, combinations thereof,and/or the like. In some embodiments, a frustule 50 includes materialcomprising ZnO. In some embodiments, a frustule 50 includes a materialcomprising a semiconductor material, including silicon, germanium,silicon germanium, gallium arsenide, combinations thereof, and/or thelike. The surface modifying material may be on an exterior surfaceand/or an interior surface of the frustules 50. In some embodiments,frustules 50 comprise a surface modifying material on all orsubstantially all of the surfaces of the frustules 50.

A material can be formed or deposited onto a surface of a frustule 50 inpart through combining a frustule 50 with a formulation including adesired material to allow coating or seeding of the material onto asurface of the frustule 50.

As described herein, a material may be deposited onto a surface of thefrustule 50. In some embodiments, the material comprises a conductivemetal such as silver, aluminum, tantalum, copper, lithium, magnesium,and brass. In some embodiments, coating a surface of the frustule 50with a material comprising silver includes, at least in part, combiningthe frustule 50 with a solution comprising ammonia (NH₃) and silvernitrate (AgNO₃). In some embodiments, the solution can be prepared in aprocess similar to a process often used in preparing Tollens' reagent.For example, preparation of the solution may comprise addition ofammonia to aqueous silver nitrate to form a precipitate, followed byfurther addition of ammonia until the precipitate dissolves. Thesolution may then be combined with the frustule 50. As an example, 5milliliters (mL) of ammonia may be added to 150 mL of aqueous silvernitrate while stirring such that a precipitate forms, followed byaddition of another 5 mL of ammonia until the precipitate dissolves. Amixture may then be formed by combining the solution with 0.5 grams (g)of frustules 50 and an aqueous solution of glucose (e.g., 4 g of glucosedissolved in 10 mL of distilled water). The mixture may then be placedinto a container immersed in a bath maintained at a temperature (e.g., awarm water bath maintained at a temperature of about 70° C.) so as tofacilitate the coating of the frustules 50.

Growing Nanostructures on Diatom Frustules or Portions of DiatomFrustules

As described herein, diatomaceous earth is naturally occurring sedimentfrom fossilized microscopic organisms called diatoms. The fossilizedmicroorganisms comprise hard frustules made from highly structuredsilica with sizes often between about 1 micron and about 200 microns.Different species of diatoms have different 3D shapes and features,which vary from source to source.

Diatomaceous earth can include a highly porous, abrasive, and/or heatresistant material. Due to these properties, diatomaceous earth hasfound wide applications including filtering, liquid absorption, thermalisolation, as ceramic additive, mild abrasive, cleaning, food additive,cosmetics, etc.

Diatom frustules have attractive features for nano science andnanotechnology—they have naturally occurring nanostructures: nanopores,nanocavities and nanobumps (e.g., as shown in FIGS. 1 to 3). Theabundance of frustule shapes depending on the diatom species (e.g., morethan 105) is another attractive property. Silicon dioxide, from whichthe diatom frustules are made, can be coated or replaced by a usefulsubstance while preserving the diatom nanostructures. Diatomnanostructures may serve as a useful nanomaterial for many processes anddevices: dye-sensitized solar cells, drug delivery, electroluminescentdisplays, anode for Li-ion batteries, gas sensors, biosensors, etc.Formation of MgO, ZrO₂, TiO₂, BaTiO₃, SiC, SiN, and Si may beaccomplished using high temperature gas displacement of SiO₂.

In some embodiments, diatom frustules can be coated with 3Dnanostructures. The diatoms may be coated on inner and/or outersurfaces, including inside the nanopores of the diatoms. The coatingsmay not preserve the diatom structure precisely. However, coatings maythemselves have nanopores and nanobumps. Such silicafrustules/nanostructures composites use frustules as support. Thenanostructured material may have small nanoparticles densely joinedtogether: nanowires, nanospheres, nanoplates, dense array ofnanoparticles, nanodisks, and/or nanobelts. Overall, the composites mayhave a very high surface area.

Nanostructures formed on a surface of a diatom frustule may include: 1)silver (Ag) nanostructures; 2) zinc-oxide (ZnO) nanostructures; and/or3) carbon nanotubes “forest.” As described herein, the diatom frustuleshaving nanostructures formed on one or more of their surfaces can beused for energy storage devices such as batteries and supercapacitors,solar cells, and/or gas sensors. Nanostructures may be formed on one ormore surfaces of unbroken frustules and/or broken frustules. In someembodiments, frustules or portions of frustules used in thenanostructure formation process may have been extracted through aseparation procedures comprising separation steps described herein(e.g., the separation process 20 shown in FIGS. 4A and 4B).

In some embodiments, nanostructures are grown using two step approaches.The first step generally includes the growth of seeds on the surface ofdiatom frustules. Seeds are nanostructures that are directly bonded(e.g., chemically bonded) to the surfaces of the diatom frustules, andmay have certain grain size and/or uniformity. Energy may be provided tocreate such bonds. The seeding process may be conducted under hightemperatures and/or involve other techniques that can create heat orsome other form of energy gain.

A second step of forming nanostructures generally includes growing thefinal nanostructures from the seeds. Frustules pre-coated with seeds maybe immersed in environments of initial materials under certainconditions. The nanostructures may include one or more of nanowires,nanoplates, dense nanoparticles, nanobelts, nanodisks, combinationsthereof, and/or the like. The form factor may depend on conditions ofthe growth of the nanostructures (e.g., morphology of the nanostructurescan depend on one or more growth conditions during forming of thenanostructures on the seed layer, including for example a growthtemperature, a pattern of heating, inclusion of a chemical additiveduring the nanostructure growth, and/or combinations thereof).

An Example Process of Forming Ag Nanostructures on Surfaces of DiatomFrustules

The initial coating of silica with silver (or seeding) can be realizedby reduction of a Ag⁺ salt using microwave, ultrasonication, surfacemodification, and/or reduction of silver nitrate (AgNO₃) with a reducingagent.

The seed growth step may include dissolution of a silver salt and areducing agent in a solvent (e.g., the reducing agent and the solventcan be the same substance) and dispersing purified diatoms in themixture. During and/or after the dissolution, a physical force likemixing, stirring, heating, ultrasonication, microwaves, combinationsthereof, and/or the like may be applied. The seed layer growth processmay occur for various amounts of time.

Examples of Growing Ag Seeds on Surfaces of Diatom Frustules

Example 1 includes the following steps: 0.234 g of purified diatoms, 0.1g AgNO₃, and 50 mL of molten at 60° C. PEG 600 (polyethylene glycol) aremixed in a beaker. In some embodiments, a mixture comprising cleandiatoms, a silver contributing component (e.g., silver nitrate), and areducing agent may be heated by a cyclic heating regimen. In someembodiments, the reducing agent and the solvent can be the samesubstance. For example, a mixture may be heated for about 20 minutes toabout 40, alternating the heat from about 100 Watt to about 500 Wattevery minute. For example, the mixture comprising cleaned diatoms,silver nitrate, and molten PEG was heated by microwave for about 30 min.The microwave power was altered from 100 to 500 Watt every minute toprevent overheating the mixture. Some commercial microwaves allow theuser to determine the temperature of the contents after a certainduration, and/or to determine multiple temperatures after variousdurations (e.g., to define a temperature ramp), during which themicrowave controls the power in order to achieve that result. Forexample, the microwave may determine that a lower power is needed toheat 50 mL of water to 85° C. in 2 min than to heat 50 mL of water to85° C. in 1 min, and this adjustment may be made during the heatingprocess, for example based on temperature sensors. For another example,the microwave may determine that a lower power is needed to heat 50 mLof water to 85° C. in 2 min than to heat 100 mL of water to 85° C. in 2min, and this adjustment may be made during the heating process, forexample based on temperature sensors. The diatoms were centrifuged andwashed with ethanol. The seeds are illustrated in FIGS. 5B and 5C.

Example 2 includes the following steps: Mix 45 mL ofN,N-dimethylformamide, 0.194 g of 6,000 MW PVP (polyvinylpyrrolidone), 5mL of 0.8 mM AgNO₃ in water, and 0.1 g of filtered and purified diatomsin a beaker. A tip of an ultrasonic processor (e.g., 13 mm diameter, 20kHz, 500 Watt) is placed in the mixture and the beaker with the mixtureplaced in an ice bath. Tip amplitude is set at 100%. Sonication lasts 30min. The diatoms are cleaned after the procedure in ethanol two timesusing bath sonication and centrifugation at 3,000 RPM for 5 min. Thenthe process is repeated two more times until seeds are seen on thediatoms.

FIG. 5B shows a SEM image, at 50 k× magnification, of silver seeds 62formed on a surface of a diatom frustule 60. FIG. 5C shows a SEM image,at 250 k× magnification, of the silver seeds 62 formed on the surface ofthe diatom frustule 60.

Example of Forming Silver Nanostructures on Silver Seeded DiatomFrustule Surfaces

Further coating of the seeded frustules with silver may be conductedunder argon (Ar) atmosphere to inhibit formation of silver oxides. Insome embodiments, diatom frustule portions can be sintered (e.g., heatedto a temperature of about 400° C. to about 500° C.) to obtain silverfrom silver oxides which may have formed on one or more surfaces ofdiatom frustule portions, including silver oxides formed during theprocess to further coat the seeded diatom frustule portions with silver.For example, sintering of diatom frustule portions may be performed ondiatom frustule portions used in fabricating a conductive silver ink(e.g., a UV-curable conductive silver ink as described herein). In someembodiments, the sintering may be under an atmosphere configured topromote reduction of silver oxides to silver (e.g., hydrogen gas).Sintering the diatom frustule portions that the conductive silver inkcomprises to obtain silver from silver oxides may improve conductivityof the conductive silver ink, for example because silver is moreconductive than silver oxide and/or because silver-silver contact (e.g.,as opposed to silver-silver oxide contact and/or silver oxide-silveroxide contact) may be increased. Other methods of obtaining silver fromsilver oxide may also be suitable in place of or in combination withsintering, including, for example, a process comprising a chemicalreaction.

Formation of nanostructures on the seed layer may include a silver salt,a reducing agent, and a solvent. A mixing step, a heating step, and/or atitration step (e.g., to facilitate interaction of components of thenanostructure growth process) may be applied to form the nanostructureson the seed layer.

An example of process for forming the nanostructures on the seed layer(e.g., forming a thick silver coating) includes the following process:

5 mL of 0.0375 M PVP (6,000 MW) solution in water is placed in onesyringe and 5 mL of 0.094 M AgNO₃ solution in water is placed in anothersyringe. 0.02 g of seeded washed and dried diatoms mixed with 5 mL ofethylene glycol heated to about 140° C. The diatoms are titrated withsilver salt (e.g., AgNO₃) and PVP solutions at a rate of about 0.1milliliter per minute (mL/min) using a syringe pump. After the titrationis finished, the mixture is stirred for about 30 min. Then diatoms arewashed (e.g., washed two times) using ethanol, bath sonication, andcentrifugation.

FIGS. 5D and 5E show SEM images of an example where silvernanostructures 64 have formed on a surface of diatom frustule 60. FIGS.5D and 5E show a frustule 60 having a thick nanostructured coating withhigh surface area. FIG. 5D is a SEM image of the frustule surface at 20k× magnification, while FIG. 5E shows a SEM image of the frustulesurface at 150 k× times magnification.

Examples of suitable reducing agents for Ag growth include commonreducing agents used for silver electroless deposition. Some suitablereducing agents for silver electroless deposition include hydrazine,formaldehyde, glucose, sodium tartrate, oxalic acid, formic acid,ascorbic acid, ethylene glycol, combinations thereof, and/or the like.

Examples of suitable Ag⁺ salts and oxides include silver salts. The mostcommonly used silver salts are soluble in water (e.g., AgNO₃). Suitablesilver salts may include an ammonium solution of AgNO₃ (e.g.,Ag(NH₃)₂NO₃). In some embodiments, any silver (I) salt or oxide can beused (e.g., soluble and/or not soluble in water). For example, silveroxide (Ag₂O), silver chloride (AgCl), silver cyanide (AgCN), silvertetrafluoroborate, silver hexafluorophosphate, silver ethylsulphate,combinations thereof, and/or the like, may also be suitable.

Suitable solvents may include: water, alcohols such as methanol,ethanol, N-propanol (including 1-propanol, 2-propanol (isopropanol orIPA), 1-methoxy-2-propanol), butanol (including 1-butanol, 2-butanol(isobutanol)), pentanol (including 1-pentanol, 2-pentanol, 3-pentanol),hexanol (including 1-hexanol, 2-hexanol, 3-hexanol), octanol, N-octanol(including 1-octanol, 2-octanol, 3-octanol), tetrahydrofurfuryl alcohol(THFA), cyclohexanol, cyclopentanol, terpineol; lactones such as butyllactone; ethers such as methyl ethyl ether, diethyl ether, ethyl propylether, and polyethers; ketones, including diketones and cyclic ketones,such as cyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone,acetone, benzophenone, acetylacetone, acetophenone, cyclopropanone,isophorone, methyl ethyl ketone; esters such ethyl acetate, dimethyladipate, proplyene glycol monomethyl ether acetate, dimethyl glutarate,dimethyl succinate, glycerin acetate, carboxylates; carbonates such aspropylene carbonate; polyols (or liquid polyols), glycerols and otherpolymeric polyols or glycols such as glycerin, diol, triol, tetraol,pentaol, ethylene glycols, diethylene glycols, polyethylene glycols,propylene glycols, dipropylene glycols, glycol ethers, glycol etheracetates 1,4-butanediol, 1,2-butanediol, 2,3-butanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol,1,2-propanediol, 1,3-butanediol, 1,2-pentanediol, etohexadiol,p-menthane-3,8-diol, 2-methyl-2,4-pentanediol; tetramethyl urea,n-methylpyrrolidone, acetonitrile, tetrahydrofuran (THF), dimethylformamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO);thionyl chloride; sulfuryl chloride, combinations thereof, and/or thelike.

In some embodiments, a solvent can also act as a reducing agent.

Example Method of Fabricating A Low-Cost UV-Curable Silver-DiatomConductive Ink

Thermally curable silver flake and silver nanoparticle conductive inksare available from a variety of manufacturers such as Henkel Corp.,Spraylat Corp., Conductive Compounds, Inc., DuPont, Inc., CreativeMaterials Corp., et al. A much less common product is a silverconductive ink curable with ultraviolet (UV) light. Only a fewsuppliers, (e.g., Henkel Corp.) have such inks in their productofferings. UV-curable silver conductive inks often can be very costlybecause of the high silver loading, and high cost per square meterrelative to the conductivity. The conductivities can be as much as 5 to10 times lower than thermally cured silver conductive inks applied atthe same wet film thickness.

There is clearly a need for a low-cost UV-curable silver with at leastthe same or better conductivity than the currently available UV-curableinks. Some UV-curable silvers may not take full advantage of the volumeof silver present in the ink, so there is a need to develop a silver inkusing much less silver that has similar or better conductivity and/orcurability than current UV-curable silver inks.

A difficulty with developing UV-curable silvers may be due to the UVabsorption properties of silver. In thermally-cured silver inks, silverflakes having a high aspect ratio may be used to produce the highestconductivity by maximizing the inter-flake contact area. If this type ofsilver flake is mixed with a UV-curable resin system appropriate for aconductive ink, applied to a surface using printing or other coatingprocesses, and then exposed to UV light, most of the UV light may beabsorbed by the silver before the UV light can scatter through the wetlayer of silver ink. UV absorption by silver flakes can impede orprevent UV light-initiated polymerization from occurring in the wet inkfilm (e.g., impeding or preventing UV light-initiated polymerization ofthe wet ink beyond a certain depth). Reduced polymerization of the inkfilm may result in an incompletely cured layer of silver ink that maynot adhere to the substrate, for example due to the bottom-most portionsof the silver ink layer being uncured and wet. Lower aspect-ratio silverparticles may be used in UV-curable silver inks to obtain suitablecuring throughout the applied layer of silver ink by increasing thenumber of possible light scattering paths through the applied layer ofsilver ink. The low aspect-ratio particles have decreased surface area,which may reduce inter-flake contact area, and in turn may reduceconductivity of the cured film relative to what would be possible if ahigh aspect-ratio flake was used. If this curing problem could besolved, larger aspect ratio silver flake with higher conductivity couldbe used in the silver ink, which may improve conductivity of theresulting silver film and/or reduce the amount of silver used to achievea high conductivity.

In some embodiments, a non-conducting substrate (e.g., a diatom frustuleportion, such a diatom frustule flake) can be plated with silver. UVlight may pass through the perforations on one or more surfaces of thebody of the diatom frustule flake. Using the silver plated diatom flakein the silver ink may facilitate curing of the silver ink, enabling theuse of high aspect ratio flakes in the silver ink. In some embodiments,a silver ink comprising silver plated diatom frustules may enableincreased conductivity of the cured silver ink while, at the same time,reducing the cost of the ink.

In some embodiments, the portions of diatom frustules (e.g., brokendiatom frustules) used in the silver ink can be purified and separatedfrom the intact diatom particles, and one or more surfaces of theportions of diatom frustules may be electrolessly coated with silver,for example according to methods described herein.

A diatom surface may be perforated by a regular pattern of holes oropenings (e.g., including holes approximately 300 nm in diameter), evenwhen coated with silver. The openings may be large enough to allow UVwavelengths to scatter through the silver coated diatom particles.Broken diatoms coated with silver may comprise shards in the form ofhigh aspect-ratio perforated flakes. FIG. 5F shows a SEM image of abroken piece of diatom frustule (e.g., a diatom frustule flake 60A)coated with Ag nanostructures (e.g., silver nanostructures 64).

In some embodiments, a silver coated perforated diatom flake can be usedfor making a UV-silver ink which can be cured when a moderately thicklyink is used (e.g., a silver ink having a thickness of about 5 μm toabout 15 μm), even though the conductive particles have highaspect-ratios and therefore large surface areas. Large surface areas ofthe frustule flake may create excellent inter-flake conductivity byincreasing the number of inter-flake electrical contacts, resulting in ahighly conductive ink that uses substantially only as much silver as isneeded to achieve the desired sheet conductivity, with the rest of thevolume taken up by the inexpensive diatom filler material and UV binderresin.

The silver nanostructure may cover substantially all surfaces of thefrustules, including the inner surfaces of the frustule perforations,but without blocking the perforations (e.g., one or more surfaces of theperforations and frustule surfaces may be plated with silvernanostructures and/or a silver seed layer). The perforations in the Agcoated diatom flakes may allow UV radiation to pass through the diatomflakes, facilitating curing to a deep depth within the applied silverink films while allowing current to be conducted directly from one sideof the flake to the other through the perforations. A reduction in thelength of the conduction pathways through the flake may reduce theoverall resistance of the cured film made from the silver ink.

An example UV light-induced polymerizable ink formulation may includecomponents from the following list. In some embodiments, a silver inkhaving diatom frustule flakes can be fabricated by combining componentslisted below, including, for example, combining a plurality of frustuleportions (e.g., frustule flakes) having silver nanostructures formed onone or more surfaces with one or more other silver ink components listedbelow. A silver film may be fabricated by curing the silver ink with aUV light source.

1) Diatoms, any of a variety of species, plated (e.g., havingnanostructure formed thereon) with between about 10 nm and about 500 nmthick Ag coating. A thickness of the Ag coating may depend on a poresize of the diatom perforations. Ratios in the formulation may bebetween about 50% and about 80% by weight. An example diatom specieswhose fragments can be used is Aulacoseira sp. 1.

2) A polar vinyl monomer with good affinity for silver, such asn-vinyl-pyrrolidone or n-vinylcaprolactam.

3) An acrylate oligomer with good elongation properties as a rheologymodifier and to improve flexibility in the cured film.

4) One or more difunctional or trifunctional acrylate monomers oroligomers as crosslinking agents to produce a tougher, more solventresistant cured film through increased cross-linking. These materialsmay be chosen to function as photoinitiation synergists, which mayimprove surface curing. Examples may include ethoxylated or propoxylatedhexandiol acrylates such as Sartomer CD560®, ethoxylatedtrimethylpropane triacrylate available, for example from Sartomer underthe product code SR454®, or triallyl cyanurate available, for examplefrom Sartomer under the product code SR507A®. Acrylated amine synergistsmay be an option, and examples may include Sartomer CN371® and SartomerCN373®.

5) An acrylate-based flow and level agent to reduce bubbling and improvewet ink quality (e.g., suitable flow and level agents may includeModaflow 2100®, Modaflow 9200®). Improved wet ink quality may, in turn,improve cured silver ink film quality.

6) One or more photoinitiators appropriate for pigment loaded inksystems. In some embodiments, at least one of the photoinitatiors issensitive to wavelengths near to or smaller than the silver plateddiatom flake's average pore size so that UV photons may pass through thepore in order to initiate polymerization underneath the flake and/orscatter through a perforation in another silver plated diatom flake topenetrate even deeper into the uncured film to initiate polymerizationthere. Examples of photoinitiators can include Ciba Irgacure 907® andIsopropyl thioxothanone (ITX, available from Lambson, UK under thetradename Speedcure ITV)).

7) An optional adhesion promoting acrylate (e.g., 2-carboxyethylacrylate).

8) A optional wetting agent to lower surface tension and improve flakewetting (e.g., DuPont Capstone FS-30® and DuPont Capstone FS-31®).

9) An optional UV stabilizer to suppress premature polymerizationtriggered by the presence of silver metal (e.g., hydroquinone and methylethyl hydroquinone (MEHQ)).

10) An optional low boiling point solvent for lowering viscosity tofacilitate the silver ink formulation being used in high speed coatingprocesses, including processes such flexographic printing, gravureprinting, combinations thereof, and/or the like.

In some embodiments, a silver ink comprising diatom frustule portionscan be thermally cured. In some embodiments, the silver ink can beexposed to a heat source. For example, the silver ink may be heated tofacilitate a polymerization reaction between polymer components of thesilver ink. In some embodiments, thermal curing of the silver ink canfacilitate removal of a solvent component. For example, the silver inkcan be exposed to a heat source to raise a temperature of the silver inkabove a boiling point of the silver ink solvent component to facilitateremoval of the solvent component.

An Example Process of Forming Zinc-Oxide (ZnO) Nanostructures onSurfaces of Diatom Frustules

Generally, the ZnO seeds on a substrate can be deposited using spray orspin coating of colloidal ZnO or with thermal decomposition of zincsalts solutions. For example, thermal decomposition of zinc acetateprecursor can give vertically well-aligned ZnO nanowires.

Growth of ZnO nanostructures from seeds may be realized by thehydrolysis of Zn salts in a basic solution. The process can be performedat room temperature or at higher temperatures. Microwave heating cansignificantly accelerate growth of nanostructures. Depending on growthparameters, different nanostructures were observed (e.g., morphology ofthe nanostructures can depend on one or more growth conditions duringforming of the nanostructures on the seed layer, including for example agrowth temperature, a pattern of heating, inclusion of a chemicaladditive during the nanostructure growth, and/or combinations thereof).For example, a chemical additive may be used to achieve a desiredmorphology of nanostructures. ZnO nanostructures also can be doped tocontrol their semiconducting properties.

Example Process for Growing ZnO Seeds on Surfaces of Diatom Frustules

1. Building seeds of ZnO can be realized by heating a mixture of 0.1 gof purified diatoms and 10 mL of 0.005 M Zn(CH₃COO)₂ (e.g., a zinccontributing component) in ethanol to about 200° C. (e.g., includingfrom about 175° C. to about 225° C.) until dry. SEM images, each at 100k× magnification, of a ZnO seeded frustule surface are shown in FIGS. 5Gand 5H. FIGS. 5G and 5H show SEM images of seeds 72 comprising ZnOformed on a surface of a frustule 70. FIG. 5G shows a SEM image, at 100k× magnification, of a frustule surface having seeds 72 comprisingzinc-oxide. FIG. 5H shows a SEM image, at 100 k× magnification, of afrustule surface having seeds 72 comprising zinc-oxide.

Example Process for Growing ZnO Nanostructures on ZnO Seeded Surfaces ofDiatom Frustules

2. ZnO nanostructures growth was conducted in mixture of 0.1 g seededfrustules with 10 mL of 0.025 M ZnNO₃ (e.g., a zinc contributingcomponent) and 0.025 M hexamethylenetetramine solution (e.g., a basicsolution) in water. The mixture was heated to about 90° C. (e.g.,including from about 80° C. to about 100° C.) for about two hours (e.g.,including from about one hour to about three hours) on a stir plate, orby using a cyclic heating routine (e.g., microwave heating) for aduration of about 10 min (e.g., including for a duration of about 5minutes to about 30 minutes) where the sample is heated by about 500Watt of power (e.g., including from about 480 Watt to about 520 Watt)for about 2 min (e.g., including about 30 seconds to about 5 minutes,about 1 minute to about 5 minutes, about 5 minutes to about 20 minutes)and then heating is turned off for about 1 min (e.g., including fromabout 30 seconds to about 5 minutes) before repeating the heating at 500Watt. The resulting nanowires 74 on the inside and outside surfaces of afrustule 70 are shown in FIGS. 5I and 5J. FIG. 5I shows a SEM image, at50 k× magnification, of ZnO nanowires 74 formed on both inside surfacesand outside surfaces of a diatom frustule 70. In some embodiments, ZnOnanowires 74 can be formed on a portion of a surface on an interior of adiatom frustule 70. For example, ZnO nanowires 74 may be formed on allor substantially all surfaces on an interior of a diatom frustule 70.ZnO nanowires 74 may be formed on all or substantially all interior andexterior surfaces of a diatom frustule 70. The drawings of thisapplication provide proof that growth of nanostructures (e.g., ZnOnanowires) on diatom frustules is possible, including growth ofnanostructures (e.g., ZnO nanowires) on the inside of diatom frustules.Coating all or substantially all sides of the diatom frustules with ZnOnanostructures may provide increase conductivity of a material (e.g.,ink or a layer printed therefrom) comprising the ZnOnanostructure-coated diatom frustules (e.g., an increased bulkconductivity and/or sheet conductivity), for example in comparison tomaterials (e.g., ink or a layer printed therefrom) comprising ZnOnanostructures formed only on the outside of a substrate. FIG. 5J showsa SEM image, at 25 k× magnification, of ZnO nanowires 74 formed onsurfaces of a diatom frustule 70. When the heating was performed in amicrowave at 100 Watt (e.g., including from about 80 Watt to about 120Watt; and at about 2 min on, then about 1 min off, and repeated for atotal duration of about 10 min), nanoplates 76 can be formed on asurface of the frustules 70 (e.g., as shown in FIG. 5K).

Examples of suitable Zn salts which can be used for both ZnO seeding andnanostructures growth include: zinc acetate hydrate, zinc nitratehexahydrate, zinc chloride, zinc sulfate, sodium zincate, combinationsthereof, and/or the like.

Examples of suitable bases for ZnO nanostructures growth may include:sodium hydroxide, ammonium hydroxide, potassium hydroxide,teramethylammonium hydroxide, lithium hydroxide, hexamethylenetetramine,ammonia solutions, sodium carbonate, ethylenediamine, combinationsthereof, and/or the like.

Examples of suitable solvents for formation of ZnO nanostructuresinclude one or more alcohols. Solvents described herein as beingsuitable for Ag nanostructures growth may also be suitable for ZnOnanostructure formation.

Examples of additives that may be used for nanostructures morphologycontrol may include tributylamine, triethylamine, triethanolamine,diisopropylamine, ammonium phosphate, 1,6-hexadianol,triethyldiethylnol, isopropylamine, cyclohexylamine, n-butylamine,ammonium chloride, hexamethylenetetramine, ethylene glycol, ethanoamine,polyvinylalcohol, polyethylene glycol, sodium dodecyl sulphate,cetyltrimethyl ammonium bromide, carbamide, combinations thereof, and/orthe like.

Example Process of Forming Carbon Nanotubes on a Surface of A DiatomFrustule

Carbon nanotubes (e.g., multiwall and/or single-wall) can be grown on adiatom surface (e.g., inside and/or outside) by chemical vapordeposition technique and its varieties. In this technique, the diatomsare firstly coated with catalyst seeds and then a mixture of gases isintroduced. One of the gases may be a reducing gas and another gas maybe a source of carbon. In some embodiments, a mixture of gases may beused. In some embodiments, a neutral gas can be included for theconcentration control (e.g., argon). Argon may also be used to carryliquid carbonaceous material (e.g., ethanol). The seeds for forming acarbon nanotube can be deposited as metals by such techniques as spraycoating and/or introduced from a liquid, a gas, and/or a solid andreduced later under elevated temperatures by pyrolysis. The reduction ofcarbonaceous gases may occur at higher temperatures, for example in arange of about 600° C. to about 1100° C.

Both the seed coating process and gas reactions can be realized onfrustules surfaces due to nanoporosity. Techniques have been developedfor carbon nanotubes “forest” growth on different substrates includingsilicon, alumina, magnesium oxide, quartz, graphite, silicon carbide,zeolite, metals, and silica.

Examples of suitable metal compounds for growth of catalyst seeds caninclude nickel, iron, cobalt, cobalt-molibdenium bimetallic particles,copper (Cu), gold (Au), Ag, platinum (Pt), palladium (Pd), manganese(Mn), aluminum (Al), magnesium (Mg), chromium (Cr), antimony (Sn),aluminum-iron-molybdenum (Al/Fe/Mo), Iron pentacarbonyl (Fe(CO)₅), iron(III) nitrate hexahydrate (Fe(NO₃)₃.6H₂O), iron (III) nitratehexahydrate (CoCl₂.6H₂O) ammonium molybdate tetrahydrate((NH₄)₆Mo₇O₂₄.4H₂O), ammonium molybdate tetrahydrate ((NH₄)₆Mo₇O₂₄.4H₂O)(MoO₂Cl₂) alumina nanopowder, mixtures thereof, and/or the like.

Examples of suitable reducing gases may include ammonia, nitrogen,hydrogen, mixtures thereof, and/or the like.

Examples of suitable gases which may serve as a source of carbon (e.g.,carbonaceous gases) may include acetylene, ethylene, ethanol, methane,carbon oxide, benzene, mixtures thereof, and/or the like.

Combination of Coatings

In some embodiments, a combination of coating can also be possible. Forexample, a surface of a frustule may include both a nickel coating and acoating of carbon nanotubes (e.g., such a frustule can be used forenergy storage devices, including supercapacitors).

FIG. 6 schematically illustrates an example embodiment of an energystorage device 100. FIG. 6 may be a cross-section or elevational view ofthe energy storage device 100. The energy storage device 100 includes afirst electrode 140 and a second electrode 150, for example a cathodeand an anode, respectively or irrespectively. The first and secondelectrodes 140, 150 are separated by a separator 130. The energy storagedevice 100 may optionally include one or more current collectors 110,120 electrically coupled to one or both of the electrodes 140, 150.

In some embodiments, the energy storage device 100 comprises a firstelectrode 140, a second electrode 150, and/or a separator 130, any ofwhich may be a membrane or layer, including a deposited membrane orlayer.

A current collector 110, 120 may include any component that provides apath for electrons to external wiring. For example, a current collector110, 120 may be positioned adjacent to the surface of the first andsecond electrodes 140, 150 to allow energy flow between the electrodes140, 150 to be transferred to an electrical device. In the embodimentshown in FIG. 6, a first current collector layer 110 and a secondcollector layer 120 are adjacent to the surface of the first electrode140 and to the surface of the second electrode 150, respectively. Thecurrent collectors 110, 120 are adjacent to surfaces opposite tosurfaces of the electrode 140, 150, respectively, that are adjacent tothe separator layer 130.

In some embodiments, an energy storage device 100 includes at least onelayer or membrane comprising frustules. For example, an energy storagedevice 100 may include a layer or membrane comprising a dispersionincluding frustules. The layer or membrane comprising frustules mayinclude, for example, the first electrode 140, the second electrode 150,the separator 130, the first collector layer 110, the second collectorlayer 120, combinations thereof, and/or the like. In some embodiments,the energy storage device 100 includes frustules having a uniform orsubstantially uniform shape, dimension (e.g., diameter, length),material, porosity, a surface modifying material and/or structure, anyother suitable feature or attribute, combinations thereof, and/or thelike. In embodiments in which a plurality of layers of the energystorage 100 device comprise frustules, the frustules may be the same orsubstantially the same (e.g., having similar dimensions) or may bedifferent (e.g., insulating in the separator 130 and conductively coatedin an electrode 140, 150).

The energy storage device 100 may include one or more layers ormembranes comprising frustules having a length in a range from about 1μm to about 50 μm, from about 1 μm to about 40 μm, from about 1 μm toabout 30 μm, from about 1 μm to about 20 μm, from about 1 μm to about 10μm, from about 5 μm to about 50 μm, from about 5 μm to about 40 μm, fromabout 5 μm to about 30 μm, from about 5 μm to about 20 μm, and fromabout 5 μm to about 10 μm. In some embodiments, the cylindrically shapedfrustules have a length of no more than about 50 μm, no more than about40 μm, no more than about 30 μm, no more than about 20 μm, no more thanabout 15 μm, no more than about 10 μm, or no more than about 5 μm. Otherfrustule lengths are also possible.

The energy storage device 100 may comprise one or more layers ormembranes comprising frustules having diameters within a range of fromabout 1 μm to about 50 μm, from about 1 μm to about 40 μm, from about 1μm to about 30 μm, from about 1 μm to about 20 μm, from about 1 μm toabout 10 μm, from about 5 μm to about 50 μm, from about 5 μm to about 40μm, from about 5 μm to about 30 μm, from about 5 μm to about 20 μm, andfrom about 5 μm to about 10 μm. In some embodiments, the cylindricallyshaped frustules have a diameter of no more than about 50 μm, no morethan about 40 μm, no more than about 30 μm, no more than about 20 μm, nomore than about 15 μm, no more than about 10 μm, no more than about 5μm, no more than about 2 μm, or no more than about 1 μm. Other frustulediameters are also possible.

The energy storage device 100 may comprise frustules having a uniform orsubstantially uniform within-frustule porosity and/orfrustule-to-frustule porosity and/or frustules having porosity within aparticular range. In some embodiments, the energy storage device 100comprises one or more layers or membranes including frustules havingporosities in a range of from about 10% to about 50%, from about 15% toabout 45%, and from about 20% to about 40%. Other frustule porositiesare also possible.

As described herein, an energy storage device 100 may include one ormore layers or membranes including frustules 50 comprising no orsubstantially no surface modifying material and/or surface modifyingstructures 52 applied or formed on a surface of the frustules 50 and/orfrustules 50 comprising a material and/or structures 52 applied orformed on a surface of the frustules 50 to modify a characteristic orattribute of the frustules 50. For example, the separator 130 maycomprise frustules 50 comprising no or substantially no surfacemodifying material and/or surface modifying structures 52 applied orformed on a surface of the frustules 50, and at least one of theelectrodes 140, 150 may comprise frustules 50 comprising a materialand/or structures 52 applied or formed on a surface of the frustules 50to modify a characteristic or attribute of the frustules 50. For anotherexample, the separator 130 may comprise some frustules 50 comprising noor substantially no surface modifying material and/or surface modifyingstructures 52 applied or formed on a surface of the frustules 50 andsome frustules 50 comprising a material and/or structures 52 applied orformed on a surface of the frustules 50 to modify a characteristic orattribute of the frustules 50.

In some embodiments, the energy storage device 100 comprises frustuleshaving a non-uniform or substantially non-uniform shape, dimension,porosity, surface modifying material and/or structure, another suitableattribute, and/or combinations thereof.

FIG. 7 shows an example embodiment of a separator layer or membrane 300that may form part of an energy storage device 100. The separator 300includes frustules 320. In some embodiments, an energy storage device100 (FIG. 6) includes a separator layer or membrane 300 comprisingfrustules 320. For example, an energy storage device 100 may include aseparator 300 comprising a dispersion including frustules 320. Asdescribed herein, the frustules 320 may be sorted according to a shape,dimensions, material, porosity, combinations thereof, and/or the like,such that the separator 300 comprises frustules 320 having a uniform orsubstantially uniform shape, dimension (e.g., length, diameter),porosity, material, combinations thereof, and/or the like. For example,the separator 300 may include frustules 320 having a cylindrical orsubstantially cylindrical shape (e.g., as shown in FIG. 7), a sphericalor substantially spherical shape, another shape, and/or combinationsthereof. In some embodiments, the separator 300 includes frustules 320having a material and/or structures applied or formed on a surface ofthe frustules 320. The separator 300 may comprise frustules 320comprising no or substantially no surface modifying material and/orsurface modifying structures applied or formed on a surface of thefrustules 320 (e.g., as illustrated in FIG. 7). The separator 300 maycomprise frustules 320 comprising a material and/or structures appliedor formed on a surface of the frustules 320 to modify a characteristicor attribute of the frustules 320. The separator 300 may comprise somefrustules 320 comprising no or substantially no surface modifyingmaterial and/or surface modifying structures applied or formed on asurface of the frustules 320 and some frustules 320 comprising amaterial and/or structures applied or formed on a surface of thefrustules 320 to modify a characteristic or attribute of the frustules320.

The separator 300 may comprise frustules 320 having a mechanicalstrength sufficient to enable a stable or substantially stableseparation between a first electrode 140 and a second electrode 150 ofan energy storage device 100 (FIG. 6). In some embodiments, theseparator 300 comprises frustules 320 configured to increase efficiencyof an energy storage device 100, for example by enabling a reducedseparation distance between a first electrode 140 and a second electrode150 and/or by facilitating flow of ionic species between a firstelectrode 140 and a second electrode 150. For example, frustules 320 mayhave a uniform or substantially uniform shape, dimension, porosity,surface modifying material and/or structures, combinations thereof,and/or the like, for improved energy storage device efficiency and/ormechanical strength. The separator 300 of an energy storage device 100may comprise cylindrical or substantially cylindrical frustules 320including walls having a desired porosity, dimensions, and/or surfacemodifying material and/or structures.

The separator 300 may comprise one or more layers of frustules 320. Theseparator 300 comprising frustules 320 may have a uniform orsubstantially uniform thickness. In some embodiments, thickness of aseparator 300 comprising frustules 320 is as thin as possible. In someembodiments, thickness of a separator 300 comprising frustules 320 isfrom about 1 μm to about 100 μm, including from about 1 μm to about 80μm, from about 1 μm to about 60 μm, from about 1 μm to about 40 μm, fromabout 1 μm to about 20 μm, from about 1 μm to about 10 μm, from about 5μm to about 60 μm, from about 5 μm to about 40 μm, from about 5 μm toabout 20 μm, from about 5 μm to about 15 μm, from about 5 μm to about 10μm, from about 10 μm to about 60 μm, from about 10 μm to about 40 μm,from about 10 μm to about 20 μm, from about 10 μm to about 15 μm, andfrom about 15 μm to about 30 μm. In some embodiments, a separatorcomprises a thickness of less than about 100 μm, less than about 90 μm,less than about 80 μm, less than about 70 μm, less than about 60 μm,less than about 50 μm, less than about 40 μm, less than about 30 μm,less than about 20 μm, less than about 15 μm, less than about 10 μm,less than about 5 μm, less than about or 2 μm, less than about or 1 μm,and including ranges bordering and including the foregoing values. Otherthicknesses of the separator 300 are also possible. For example, theseparator 300 may comprise a single layer of frustules 320 such that thethickness of the separator 300 may depend at least in part on adimension of the frustules 320 (e.g., a longest axis, a length, or adiameter).

The separator 300 may comprise frustules 320 having a non-uniform orsubstantially non-uniform shape, dimension, porosity, surface modifyingmaterial and/or structure, combinations thereof, and/or the like.

In some embodiments, the separator 300 comprises a material configuredto reduce electrical resistance between a first electrode 140 and asecond electrode 150 of an energy storage device 100. For example,referring again to FIG. 7, in some embodiments, the separator 300comprises an electrolyte 340. The electrolyte 340 may include anymaterial that facilitates the conductivity of ionic species, including,for example, a material comprising mobile ionic species that can travelbetween a first electrode 140 and a second electrode 150 of an energystorage device 100. The electrolyte 340 may comprise any compound thatmay form ionic species, including but not limited to sodium sulfate(Na₂SO₄), lithium chloride (LiCl), and/or potassium sulfate (K₂SO₄). Insome embodiments, the electrolyte 340 comprises an acid, a base, or asalt. In some embodiments, the electrolyte 340 comprises a strong acid,including but not limited to sulfuric acid (H₂SO₄) and/or phosphoricacid (H₃PO₄), or a strong base, including but not limited to sodiumhydroxide (NaOH) and/or potassium hydroxide (KOH). In some embodiments,the electrolyte 340 comprises a solvent having one or more dissolvedionic species. For example, the electrolyte 340 may comprise an organicsolvent. In some embodiments, the electrolyte 340 includes an ionicliquid or an organic liquid salt. The electrolyte 340 may comprise anaqueous solution having an ionic liquid. The electrolyte 340 maycomprise a salt solution having an ionic liquid. In some embodiments,the electrolyte 340 comprising an ionic liquid includes propylene glycoland/or acetonitrile. In some embodiments, the electrolyte 340 comprisingan ionic liquid includes an acid or base. For example, the electrolyte340 may comprise an ionic liquid combined with potassium hydroxide(e.g., addition of a 0.1 M solution of KOH).

In some embodiments, the separator 300 comprises a polymer 360, such asa polymeric gel. The polymer 360 may be combined with an electrolyte340. A suitable polymer 360 may exhibit electrical and electrochemicalstability, for example maintaining integrity and/or functionality whencombined with an electrolyte 340, during electrochemical reactions,and/or subjected to an electric potential (e.g., an electric potentialexisting between the electrodes 140, 150 of the energy storage device100). The separator 300 may include a polymer 360 comprising, forexample, poly(vinylidene fluoride), poly(ethylene oxide),poly(acrylonitrile), poly(vinyl alcohol), poly(methyl methacrylate),poly(vinyl chloride), poly[bis(methoxy ethoxy ethoxyphosphazene)],poly(vinyl sulfone), poly(vinyl pyrrolidone), poly(propylene oxide),copolymers thereof, combinations thereof, and/or the like. In someembodiments, the polymer 360 comprises polytetrafluoroethylene (PTFE),including for example an aqueous solution comprising a dispersion ofPTFE in water (e.g., a Teflon® aqueous suspension). In some embodiments,the electrolyte 340 is immobilized within or on the polymer 360 to forma solid or semi-solid substance. In some such embodiments, theelectrolyte 340 is immobilized on or within a polymeric gel, for exampleto form an electrolytic gel.

In some embodiments, the separator 300 optionally comprises an adhesivematerial to enable improved adherence of frustules 320 within theseparator 300 and/or between the separator 300 and a first electrode 140and/or a second electrode 150 of an energy storage device 100. In someembodiments, the adhesive material comprises a polymer 360. For example,the adhesive material may comprise a polymer 360 that exhibitselectrical and electrochemical stability, and provides sufficientadhesion within the separator 300 and/or between the separator 300 and afirst electrode 140 and/or a second electrode 150 of an energy storagedevice 100.

FIG. 8 shows an example electrode layer or membrane 400 that may formpart of an energy storage device 100 (FIG. 6). The electrode 400includes frustules 420. In some embodiments, an energy storage device100 (FIG. 6) includes one or more electrode layers or membranes 400comprising frustules 420 (e.g., as the first electrode 140 and/or thesecond electrode 150). For example, an energy storage device 100 mayinclude an electrode layer or membrane 400 comprising a dispersionincluding frustules 420. As described herein, the frustules 420 may besorted according to a shape, dimensions, material, porosity,combinations thereof, and/or the like, such that the electrode 400comprises frustules 420 having a uniform or substantially uniform shape,dimension (e.g., length, diameter), porosity, material, combinationsthereof, and/or the like. For example, the electrode 400 may includefrustules 420 having a cylindrical or substantially cylindrical shape(e.g., as shown in FIG. 8), a spherical or substantially sphericalshape, another shape, and/or combinations thereof. In some embodiments,the electrode 400 includes frustules 420 having a material and/orstructures applied or formed on a surface of the frustules 420. Theelectrode 400 may comprise frustules 420 comprising no or substantiallyno surface modifying material, and may be insulating, and/or may havesurface modifying structures applied or formed on a surface of thefrustules 420. The electrode 400 may comprise frustules 420 comprising amaterial and/or structures applied or formed on a surface of thefrustules 420 to modify a characteristic or attribute of the frustules420 (e.g., as schematically illustrated in FIG. 8 by the chickenfoot-shaped features on the surfaces of the frustules 420). Theelectrode 400 may comprise some frustules 420 comprising no orsubstantially no surface modifying material and/or surface modifyingstructures applied or formed on a surface of the frustules 420 and somefrustules 420 comprising a material and/or structures applied or formedon a surface of the frustules 420 to modify a characteristic orattribute of the frustules 420.

The electrode 400 may comprise frustules 420 selected for mechanicalstrength such that an energy storage device 100 including the electrode400 may withstand compressive force and/or shape modifying deformation.In some embodiments, the electrode 400 comprises frustules 420configured to increase efficiency of an energy storage device 100, forexample by facilitating flow of ionic species within the electrode 400and/or between the electrode 400 and other parts of the energy storagedevice 100. For example, frustules 420 may have a uniform orsubstantially uniform shape, dimension, porosity, surface modifyingmaterial and/or structures, combinations thereof, and/or the like, forimproved energy storage device efficiency and/or mechanical strength.The electrode 400 of an energy storage device 100 may comprisecylindrical or substantially cylindrical frustules 420 including wallshaving a desired porosity, dimensions, and/or surface modifying materialand/or structures.

The electrode 400 may comprise one or more layers of frustules 420. Theelectrode 400 comprising frustules 420 may have a uniform orsubstantially uniform thickness. In some embodiments, thickness of anelectrode 400 comprising frustules 420 depends at least in part onresistance, amount of available material, desired energy devicethickness, or the like. In some embodiments, thickness of an electrode400 comprising frustules 420 is from about 1 μm to about 100 μm,including from about 1 μm to about 80 μm, from about 1 μm to about 60μm, from about 1 μm to about 40 μm, from about 1 μm to about 20 μm, fromabout 1 μm to about 10 μm, from about 5 μm to about 100 μm, includingfrom about 5 μm to about 80 μm, from about 5 μm to about 60 μm, fromabout 5 μm to about 40 μm, from about 5 μm to about 20 μm, from about 5μm to about 10 μm, from about 10 μm to about 60 μm, from about 10 μm toabout 40 μm, from about 10 μm to about 20 μm, from about 10 μm to about15 μm, and from about 15 μm to about 30 μm. In some embodiments,thickness of an electrode 400 comprising frustules 420 is less thanabout 100 μm, less than about 90 μm, less than about 80 μm, less thanabout 70 μm, less than about 60 μm, less than about 50 μm, less thanabout 40 μm, less than about 30 μm, less than about 20 μm, less thanabout 10 μm, less than about 5 μm, less than about 2 μm, or less thanabout 1 μm, and including ranges bordering and including the foregoingvalues. Other thicknesses of the separator 300 are also possible.

The electrode 400 may comprise frustules 420 having a non-uniform orsubstantially non-uniform shape, dimension, porosity, surface modifyingmaterial and/or structure, combinations thereof, and/or the like.

In some embodiments, the electrode 400 optionally comprises a materialto enhance the conductivity of electrons within the electrode 400. Forexample, referring again to FIG. 8, in some embodiments, the electrode400 comprises electrically conductive filler 460 to improve electricalconductivity within the electrode 400. Electrically conductive filler460 may comprise graphitic carbon, graphene, combinations thereof,and/or the like. In energy storage devices 100 comprising a plurality ofelectrodes 400, the electrodes 400 may include different frustulesand/or different additives, for example including different ions and/orion-producing species. In some embodiments, the electrode 400 maycomprise an electrolyte, for example the electrolyte 340 describedherein with respect to the separator 300 of FIG. 7. In some embodiments,the electrode 400 may comprise a polymer, for example the polymer 360described herein with respect to the separator 300 of FIG. 7.

In some embodiments, the electrode 400 optionally comprises an adhesivematerial to enable improved adhesion of frustules 420 within theelectrode 400 and/or between the electrode 400 and another component ofthe energy storage device 100 such as a separator 130 and/or a currentcollector 110, 120. In some embodiments, the adhesive material in theelectrode 400 comprises a polymer, for example the polymer 360 describedherein.

Example Embodiments

The following example embodiments identify some possible permutations ofcombinations of features disclosed herein, although other permutationsof combinations of features are also possible.

1. A printed energy storage device comprising:

-   -   a first electrode;    -   a second electrode; and    -   a separator between the first electrode and the second        electrode, at least one of the first electrode, the second        electrode, and the separator including frustules.

2. The device of Embodiment 1, wherein the separator includes thefrustules.

3. The device of Embodiment 1 or 2, wherein the first electrode includesthe frustules.

4. The device of any of Embodiments 1-3, wherein the second electrodeincludes the frustules.

5. The device of any one of Embodiments 1-4, wherein the frustules havea substantially uniform property.

6. The device of Embodiment 5, wherein property comprises shape.

7. The device of Embodiment 6, wherein the shape comprises a cylinder, asphere, a disc, or a prism.

8. The device of any of Embodiments 5-7, wherein the property comprisesa dimension.

9. The device of Embodiment 8, wherein the dimension comprises diameter.

10. The device of Embodiment 9, wherein the diameter is in a range fromabout 2 μm to about 10 μm.

11. The device of Embodiment 8, wherein the dimension comprises length.

12. The device of Embodiment 9, wherein the length is in a range fromabout 5 μm to about 20 μm.

13. The device of Embodiment 8, wherein the dimension comprises alongest axis.

14. The device of Embodiment 9, wherein the longest axis is in a rangefrom about 5 μm to about 20 μm.

15. The device of any of Embodiments 5-14, wherein the propertycomprises porosity.

16. The device of Embodiment 15, wherein the porosity is in a range fromabout 20% to about 50%.

17. The device of any of Embodiments 5-16, wherein the propertycomprises mechanical strength.

18. The device of any of Embodiment 1-17, wherein the frustules comprisea surface modifying structure.

19. The device of Embodiment 18, wherein the surface modifying structureincludes a conductive material.

20. The device of Embodiment 19, wherein the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass.

21. The device of any of Embodiments 18-20, wherein the surfacemodifying structure includes zinc oxide (ZnO).

22. The device of any of Embodiments 18-21, wherein the surfacemodifying structure includes a semiconductor.

23. The device of Embodiment 22, wherein the semiconductor includes atleast one of silicon, germanium, silicon germanium, and galliumarsenide.

24. The device of any of Embodiments 18-23, wherein the surfacemodifying structure comprises at least one of a nanowire, ananoparticle, and a structure having a rosette shape.

25. The device of any of Embodiments 18-24, wherein the surfacemodifying structure is on an exterior surface of the frustules.

26. The device of any of Embodiments 18-25, wherein the surfacemodifying structure is on an interior surface of the frustules.

27. The device of any of Embodiments 1-26, wherein the frustulescomprise a surface modifying material.

28. The device of Embodiment 27, wherein the surface modifying materialincludes a conductive material.

29. The device of Embodiment 28, wherein the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass.

30. The device of any of Embodiments 27-29, wherein the surfacemodifying material includes zinc oxide (ZnO).

31. The device of any of Embodiments 27-30, wherein the surfacemodifying material includes a semiconductor.

32. The device of Embodiment 31, wherein the semiconductor includes atleast one of silicon, germanium, silicon germanium, and galliumarsenide.

33. The device of any of Embodiments 27-32, wherein the surfacemodifying material is on an exterior surface of the frustules.

34. The device of any of Embodiments 37-33, wherein the surfacemodifying material is on an interior surface of the frustules.

35. The device of any of Embodiments 1-34, wherein the first electrodecomprises a conductive filler.

36. The device of any of Embodiments 1-35, wherein the second electrodecomprises a conductive filler.

37. The device of Embodiment 34 or 35, wherein the conductive fillercomprises graphitic carbon.

38. The device of any of Embodiments 35-37, wherein the conductivefiller comprises graphene.

39. The device of any of Embodiments 1-38, wherein the first electrodecomprises an adherence material.

40. The device of any of Embodiments 1-39, wherein the second electrodecomprises an adherence material.

41. The device of any of Embodiments 1-40, wherein the separatorcomprises an adherence material.

42. The device of any of Embodiments 39-41, wherein the adherencematerial comprises a polymer.

43. The device of any of Embodiments 1-42, wherein the separatorcomprises an electrolyte.

44. The device of Embodiment 43, wherein the electrolyte comprises atleast one of an ionic liquid, an acid, a base, and a salt.

45. The device of Embodiment 43 or 44, wherein the electrolyte comprisesan electrolytic gel.

46. The device of any of Embodiments 1-45, further comprising a firstcurrent collector in electrical communication with the first electrode.

47. The device of any of Embodiments 1-46, further comprising a secondcurrent collector in electrical communication with the second electrode.

48. The device of any of Embodiments 1-47, wherein the printed energystorage device comprises a capacitor.

49. The device of any of Embodiments 1-47, wherein the printed energystorage device comprises a supercapacitor.

50. The device of any of Embodiments 1-47, wherein the printed energystorage device comprises a battery.

51. A system comprising a plurality of the devices of any of Embodiments1-50 stacked on top of each other.

52. An electrical device comprising the device of any of Embodiments1-50 or the system of Embodiment 51.

53. A membrane for a printed energy storage device, the membranecomprising frustules.

54. The membrane of Embodiment 53, wherein the frustules have asubstantially uniform property.

55. The membrane of Embodiment 54, wherein the property comprises shape.

56. The membrane of Embodiment 55, wherein the shape comprises acylinder, a sphere, a disc, or a prism.

57. The membrane of any of Embodiments 54-56, wherein the propertycomprises a dimension.

58. The membrane of Embodiment 57, wherein the dimension comprisesdiameter.

59. The membrane of Embodiment 58, wherein the diameter is in a rangefrom about 2 μm to about 10 μm.

60. The membrane of any of Embodiments 54-59, wherein the dimensioncomprises length.

61. The membrane of Embodiment 60, wherein the length is in a range ofabout 5 to about 20 μm.

62. The membrane of any of Embodiments 54-61, wherein the dimensioncomprises a longest axis.

63. The membrane of Embodiment 62, wherein the longest axis is in arange of about 5 μm to about 20 μm.

64. The membrane of any of Embodiments 54-63, wherein the propertycomprises porosity.

65. The membrane of Embodiment 64, wherein the porosity is in a rangefrom about 20% to about 50%.

66. The membrane of any of Embodiments 54-65, wherein the propertycomprises mechanical strength.

67. The membrane of any of Embodiments 53-66, wherein the frustulescomprise a surface modifying structure.

68. The membrane of Embodiment 67, wherein the surface modifyingstructure includes a conductive material.

69. The membrane of Embodiment 68, wherein the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass.

70. The membrane of any of Embodiments 67-69, wherein the surfacemodifying structure includes zinc oxide (ZnO).

71. The membrane of any of Embodiments 67-70, wherein the surfacemodifying structure includes a semiconductor.

72. The membrane of Embodiment 71, wherein the semiconductor includes atleast one of silicon, germanium, silicon germanium, and galliumarsenide.

73. The membrane of any of Embodiments 67-72, wherein the surfacemodifying structure comprises at least one of a nanowire, ananoparticle, and a structure having a rosette shape.

74. The membrane of any of Embodiments 67-73, wherein the surfacemodifying structure is on an exterior surface of the frustules.

75. The membrane of any of Embodiments 67-74, wherein the surfacemodifying structure is on an interior surface of the frustules.

76. The membrane of any of Embodiments 53-75, wherein the frustulescomprises a surface modifying material.

77. The membrane of Embodiment 76, wherein surface modifying materialincludes a conductive material.

78. The membrane of Embodiment 77, wherein the conductive materialincludes at least one of silver, aluminum, tantalum, copper, lithium,magnesium, and brass.

79. The membrane of any of Embodiments 76-78, wherein the surfacemodifying material includes zinc oxide (ZnO).

80. The membrane of any of Embodiments 76-79, wherein the surfacemodifying material includes a semiconductor.

81. The membrane of Embodiment 80, wherein the semiconductor includes atleast one of silicon, germanium, silicon germanium, and galliumarsenide.

82. The membrane of any of Embodiments 76-81, wherein the surfacemodifying material is on an exterior surface of the frustules.

83. The membrane of any of Embodiments 76-82, wherein the surfacemodifying material is on an interior surface of the frustules.

84. The membrane of any of Embodiments 83-83, further comprising aconductive filler.

85. The membrane of Embodiment 84, wherein the conductive fillercomprises graphitic carbon.

86. The membrane of Embodiment 84 or 85, wherein the conductive fillercomprises graphene.

87. The membrane of any of Embodiments 53-86, further comprising anadherence material.

88. The membrane of Embodiment 87, wherein the adherence materialcomprises a polymer.

89. The membrane of any of Embodiments 53-88, further comprising anelectrolyte.

90. The membrane of Embodiment 89, wherein the electrolyte comprises atleast one of an ionic liquid, an acid, a base, and a salt.

91. The membrane of Embodiment 89 or 90, wherein the electrolytecomprises an electrolytic gel.

92. An energy storage device comprising the membrane of any ofEmbodiments 53-91.

93. The device of Embodiment 92, wherein the printed energy storagedevice comprises a capacitor.

94. The device of Embodiment 92, wherein the printed energy storagedevice comprises a supercapacitor.

95. The device of Embodiment 92, wherein the printed energy storagedevice comprises a battery.

96. A system comprising a plurality of the devices of any of Embodiments92-95 stacked on top of each other.

97. An electrical device comprising the device of any of Embodiments92-95 or the system of Embodiment 96.

98. A method of manufacturing a printed energy storage device, themethod comprising:

-   -   forming a first electrode;    -   forming a second electrode; and    -   forming a separator between the first electrode and the second        electrode, at least one of the first electrode, the second        electrode, and the separator including frustules.

99. The method of Embodiment 98, wherein the separator includes thefrustules.

100. The method of Embodiment 99, wherein forming the separator includesforming a dispersion including the frustules.

101. The method of Embodiment 99 or 100, wherein forming the separatorincludes screen printing the separator.

102. The method of Embodiment 99, wherein forming the separator includesforming a membrane including the frustules.

103. The method of Embodiment 102, wherein forming the separatorincludes roll-to-roll printing the membrane including the separator.

104. The method of any of Embodiments 98-103, wherein the firstelectrode includes the frustules.

105. The method of Embodiment 104, wherein forming the first electrodeincludes forming a dispersion including the frustules.

106. The method of Embodiment 104 or 105, wherein forming the firstelectrode includes screen printing the first electrode.

107. The method of Embodiment 104, wherein forming the first electrodeincludes forming a membrane including the frustules.

108. The method of Embodiment 107, wherein forming the first electrodeincludes roll-to-roll printing the membrane including the firstelectrode.

109. The method of any of Embodiments 98-108, wherein the secondelectrode includes the frustules.

110. The method of Embodiment 109, wherein forming the second electrodeincludes forming a dispersion including the frustules.

111. The method of Embodiment 109 or 110, wherein forming the secondelectrode includes screen printing the second electrode.

112. The method of Embodiment 109, wherein forming the second electrodeincludes forming a membrane including the frustules.

113. The method of Embodiment 112, wherein forming the second electrodeincludes roll-to-roll printing the membrane including the secondelectrode.

114. The method of any of Embodiments 98-113, further comprising sortingthe frustules according to a property.

115. The method of Embodiment 114, wherein the property comprises atleast one of shape, dimension, material, and porosity.

116. An ink comprising:

-   -   a solution; and    -   frustules dispersed in the solution.

117. The ink of Embodiment 116, wherein the frustules have asubstantially uniform property.

118. The ink of Embodiment 117, wherein the property comprises shape.

119. The ink of Embodiment 118, wherein the shape comprises a cylinder,a sphere, a disc, or a prism.

120. The ink of any of Embodiments 117-119, wherein the propertycomprises a dimension.

121. The ink of Embodiment 120, wherein the dimension comprisesdiameter.

122. The ink of Embodiment 121, wherein the diameter is in a range fromabout 2 μm to about 10 μm.

123. The ink of any of Embodiments 117-122, wherein the dimensioncomprises length.

124. The ink of Embodiment 123, wherein the length is in a range ofabout 5 μm to about 20 μm.

125. The ink of any of Embodiments 117-124, wherein the dimensioncomprises a longest axis.

126. The ink of Embodiment 125, wherein the longest axis is in a rangeof about 5 to about 20 μm.

127. The ink of any of Embodiments 117-126, wherein the propertycomprises porosity.

128. The ink of Embodiment 127, wherein the porosity is in a range fromabout 20% to about 50%.

129. The ink of any of Embodiments 117-128, wherein the propertycomprises mechanical strength.

130. The ink of any of Embodiments 116-129, wherein the frustulescomprise a surface modifying structure.

131. The ink of Embodiment 130, wherein the surface modifying structureincludes a conductive material.

132. The ink of Embodiment 131, wherein the conductive material includesat least one of silver, aluminum, tantalum, copper, lithium, magnesium,and brass.

133. The ink of any of Embodiments 130-132, wherein the surfacemodifying structure includes zinc oxide (ZnO).

134. The ink of any of Embodiments 130-133, wherein the surfacemodifying structure includes a semiconductor.

135. The ink of Embodiment 134, wherein the semiconductor includes atleast one of silicon, germanium, silicon germanium, and galliumarsenide.

136. The ink of any of Embodiments 130-135, wherein the surfacemodifying structure comprises at least one of a nanowire, ananoparticle, and a structure having a rosette shape.

137. The ink of any of Embodiments 130-136, wherein the surfacemodifying structure is on an exterior surface of the frustules.

138. The ink of any of Embodiments 130-137, wherein the surfacemodifying structure is on an interior surface of the frustules.

139. The ink of any of Embodiments 116-138, wherein the frustulescomprises a surface modifying material.

140. The ink of Embodiment 139, wherein surface modifying materialincludes a conductive material.

141. The ink of Embodiment 140, wherein the conductive material includesat least one of silver, aluminum, tantalum, copper, lithium, magnesium,and brass.

142. The ink of any of Embodiments 139-141, wherein the surfacemodifying material includes zinc oxide (ZnO).

143. The ink of any of Embodiments 139-142, wherein the surfacemodifying material includes a semiconductor.

144. The ink of Embodiment 143, wherein the semiconductor includes atleast one of silicon, germanium, silicon germanium, and galliumarsenide.

145. The ink of any of Embodiments 139-144, wherein the surfacemodifying material is on an exterior surface of the frustules.

146. The ink of any of Embodiments 139-145, wherein the surfacemodifying material is on an interior surface of the frustules.

147. The ink of any of Embodiments 116-146, further comprising aconductive filler.

148. The ink of Embodiment 147, wherein the conductive filler comprisesgraphitic carbon.

149. The ink of Embodiment 147 or 148, wherein the conductive fillercomprises graphene.

150. The ink of any of Embodiments 116-149, further comprising anadherence material.

151. The ink of Embodiment 150, wherein the adherence material comprisesa polymer.

152. The ink of any of Embodiments 116-151, further comprising anelectrolyte.

153. The ink of Embodiment 152, wherein the electrolyte comprises atleast one of an ionic liquid, an acid, a base, and a salt.

154. The ink of Embodiment 152 or 153, wherein the electrolyte comprisesan electrolytic gel.

155. A device comprising the ink of any of Embodiments 116-154.

156. The device of Embodiment 155, wherein the device comprises aprinted energy storage device.

157. The device of Embodiment 156, wherein the printed energy storagedevice comprises a capacitor.

158. The device of Embodiment 156, wherein the printed energy storagedevice comprises a supercapacitor.

159. The device of Embodiment 156, wherein the printed energy storagedevice comprises a battery.

160. A method of extracting a diatom frustule portion, the methodcomprising:

-   -   dispersing a plurality of diatom frustule portions in a        dispersing solvent;    -   removing at least one of an organic contaminant and an inorganic        contaminant;    -   dispersing the plurality of diatom frustule portions in a        surfactant, the surfactant reducing an agglomeration of the        plurality of diatom frustule portions; and    -   extracting a plurality of diatom frustule portions having at        least one common characteristic using a disc stack centrifuge.

161. The method of embodiment 160, wherein the at least one commoncharacteristic comprises at least one of a dimension, a shape, amaterial, and a degree of brokenness.

162. The method of embodiment 161, wherein the dimension comprises atleast one of a length and a diameter.

163. The method of any one of embodiments 160 to 162, wherein a solidmixture comprises the plurality of diatom frustule portions.

164. The method of embodiment 163, further comprising reducing aparticle dimension of the solid mixture.

165. The method of embodiment 164, wherein reducing the particledimension of the solid mixture is before dispersing the plurality ofdiatom frustule portions in the dispersing solvent.

166. The method of embodiment 164 or 165, wherein reducing the particledimension comprises grinding the solid mixture.

167. The method of embodiment 166, wherein grinding the solid mixturecomprises applying to the solid mixture at least one of a mortar and apestle, a jar mill, and a rock crusher.

168. The method of any one of embodiments 163 to 167, further comprisingextracting a component of the solid mixture having a longest componentdimension that is greater than a longest frustule portion dimension ofthe plurality of diatom frustule portions.

169. The method of embodiment 168, wherein extracting the component ofthe solid mixture comprises sieving the solid mixture.

170. The method of embodiment 169, wherein sieving the solid mixturecomprises processing the solid mixture with a sieve having a mesh sizefrom about 15 microns to about 25 microns.

171. The method of embodiment 169, wherein sieving the solid mixturecomprises processing the solid mixture with a sieve having a mesh sizefrom about 10 microns to about 25 microns.

172. The method of any one of embodiments 160 to 171, further comprisingsorting the plurality of diatom frustule portions to separate a firstdiatom frustule portion from a second diatom frustule portion, the firstdiatom frustule portion having a greater longest dimension.

173. The method of embodiment 172, wherein the first diatom frustuleportion comprises a plurality of unbroken diatom frustule portions.

174. The method of embodiment 172 or 173, wherein the second diatomfrustule portion comprises a plurality of broken diatom frustuleportions.

175. The method of any one of embodiments 172 to 174, wherein sortingcomprises filtering the plurality of diatom frustule portions.

176. The method of embodiment 175, wherein filtering comprisesdisturbing agglomeration of the plurality of diatom frustule portions.

177. The method of embodiment 176, wherein disturbing agglomeration ofthe plurality of diatom frustule portions comprises stirring.

178. The method of embodiment 176 or 177, wherein disturbingagglomeration of the plurality of diatom frustule portions comprisesshaking.

179. The method of any one of embodiments 176 to 178, wherein disturbingagglomeration of the plurality of diatom frustule portions comprisesbubbling.

180. The method of any one of embodiments 175 to 179, wherein filteringcomprises applying a sieve to the plurality of diatom frustule portions.

181. The method of embodiment 180, wherein the sieve has a mesh sizefrom about 5 microns to about 10 microns.

182. The method of embodiment 180, wherein the sieve has a mesh size ofabout 7 microns.

183. The method of any one of embodiments 160 to 182, further comprisingobtaining a washed diatom frustule portion.

184. The method of embodiment 183, wherein obtaining the washed diatomfrustule portion comprises washing the plurality of diatom frustuleportions with a cleaning solvent after removing the at least one of theorganic contaminant and the inorganic contaminant.

185. The method of embodiment 183 or 184, wherein obtaining the washeddiatom frustule portion comprises washing the diatom frustule portionhaving the at least one common characteristic with a cleaning solvent.

186. The method of embodiment 184 or 185, further comprising removingthe cleaning solvent.

187. The method of embodiment 186, wherein removing the cleaning solventcomprises sedimenting the plurality of diatom frustule portions afterremoving at least one of the organic contaminant and the inorganiccontaminant.

188. The method of embodiment 186 or 187, wherein removing the cleaningsolvent comprises sedimenting the plurality of diatom frustule portionshaving the at least one common characteristic.

189. The method of embodiment 187 or 188, wherein sedimenting comprisescentrifuging.

190. The method of embodiment 189, wherein centrifuging comprisesapplying a centrifuge suitable for large scale processing.

191. The method of embodiment 190, wherein centrifuging comprisesapplying at least one of a disc stack centrifuge, a decanter centrifuge,and a tubular bowl centrifuge.

192. The method of any one of embodiments 184 to 191, wherein at leastone of the dispersing solvent and the cleaning solvent comprises water.

193. The method of any one of embodiments 160 to 192, wherein at leastone of dispersing the plurality of diatom frustule portions in thedispersing solvent and dispersing the plurality of diatom frustuleportions in the surfactant comprises sonicating the plurality of diatomfrustules.

194. The method of any one of embodiments 160 to 193, wherein thesurfactant comprises a cationic surfactant.

195. The method of embodiment 194, wherein the cationic surfactantcomprises at least one of a benzalkonium chloride, a cetrimoniumbromide, a lauryl methyl gluceth-10 hydroxypropyl dimonium chloride, abenzethonium chloride, a benzethonium chloride, a bronidox, admethyldioctadecylammonium chloride, and a tetramethylammoniumhydroxide.

196. The method of any one of embodiments 160 to 195, wherein thesurfactant comprises a non-ionic surfactant.

197. The method of embodiment 196, wherein the non-ionic surfactantcomprises at least one of a cetyl alcohol, a stearyl alcohol, acetostearyl alcohol, an oleyl alcohol, a polyoxyethylene glycol alkylether, an octaethylene glycol monododecyl ether, a glucoside alkylethers, a decyl glucoside, a polyoxyethylene glycol octylphenol ethers,an octylphenol ethoxylate (Triton X-100™), a nonoxynol-9, a glyceryllaurate, a polysorbate, and a poloxamer.

198. The method of any one of embodiments 160 to 197, further comprisingdispersing the plurality of diatom frustules in an additive component.

199. The method of embodiment 198, wherein dispersing the plurality ofdiatom frustules in an additive component is before dispersing theplurality of diatom frustules in the surfactant.

200. The method of embodiment 198, wherein dispersing the plurality ofdiatom frustules in an additive component is after dispersing theplurality of diatom frustules in the surfactant.

201. The method of embodiment 198, wherein dispersing the plurality ofdiatom frustules in an additive component is at least partiallysimultaneous with dispersing the plurality of diatom frustules in thesurfactant.

202. The method of any one of embodiments 198 to 201, wherein theadditive component comprises at least one of a potassium chloride, anammonium chloride, an ammonium hydroxide, and a sodium hydroxide.

203. The method of any one of embodiments 160 to 202, wherein dispersingthe plurality of diatom frustule portions comprises obtaining adispersion comprising about 1 weight percent to about 5 weight percentof the plurality of diatom frustule portions.

204. The method of any one of embodiments 160 to 203, wherein removingthe organic contaminant comprises heating the plurality of diatomfrustule portions in the presence of a bleach.

205. The method of embodiment 204, wherein the bleach comprises at leastone of a hydrogen peroxide and a nitric acid.

206. The method of embodiment 205, wherein heating comprises heating theplurality of diatom frustule portions in a solution comprising an amountof hydrogen peroxide in a range from about 10 volume percent to about 20volume percent.

207. The method of any one of embodiments 204 to 206, wherein heatingcomprises heating the plurality of diatom frustule portions for aduration of about 5 minutes to about 15 minutes.

208. The method of any one of embodiments 160 to 207, wherein removingthe organic contaminant comprises annealing the plurality of diatomfrustule portions.

209. The method of any one of embodiments 160 to 208, wherein removingthe inorganic contaminant comprises combining the plurality of diatomfrustule portions with at least one of a hydrochloric acid and asulfuric acid.

210. The method of embodiment 209, wherein the combining comprisesmixing the plurality of diatom frustule portions in a solutioncomprising about 15 volume percent to about 25 volume percent ofhydrochloric acid.

211. The method of embodiment 210, wherein the mixing is for a durationof about 20 minutes to about 40 minutes.

212. A method of extracting a diatom frustule portion, the methodcomprising:

-   -   extracting a plurality of diatom frustule portions having at        least one common characteristic using a disc stack centrifuge.

213. The method of embodiment 212, further comprising dispersing theplurality of diatom frustule portions in a dispersing solvent.

214. The method of embodiment 212 or 213, further comprising removing atleast one of an organic contaminant and an inorganic contaminant.

215. The method of any one of embodiments 212 to 214, further comprisingdispersing the plurality of diatom frustule portions in a surfactant,the surfactant reducing an agglomeration of the plurality of diatomfrustule portions.

216. The method of any one of embodiments 212 to 215, wherein the atleast one common characteristic comprises at least one of a dimension, ashape, a material, and a degree of brokenness.

217. The method of embodiment 216, wherein the dimension comprises atleast one of a length and a diameter.

218. The method of any one of embodiments 212 to 217, wherein a solidmixture comprises the plurality of diatom frustule portions.

219. The method of embodiment 218, further comprising reducing aparticle dimension of the solid mixture.

220. The method of embodiment 219, wherein reducing the particledimension of the solid mixture is before dispersing the plurality ofdiatom frustule portions in the dispersing solvent.

221. The method of embodiment 219 or 220, wherein reducing the particledimension comprises grinding the solid mixture.

222. The method of embodiment 221, wherein grinding the solid mixturecomprises applying to the solid mixture at least one of a mortar and apestle, a jar mill, and a rock crusher.

223. The method of any one of embodiments 219 to 222, further comprisingextracting a component of the solid mixture having a longest componentdimension that is greater than a longest frustule portion dimension ofthe plurality of diatom frustule portions.

224. The method of embodiment 223, wherein extracting the component ofthe solid mixture comprises sieving the solid mixture.

225. The method of embodiment 224, wherein sieving the solid mixturecomprises processing the solid mixture with a sieve having a mesh sizefrom about 15 microns to about 25 microns.

226. The method of embodiment 224, wherein sieving the solid mixturecomprises processing the solid mixture with a sieve having a mesh sizefrom about 10 microns to about 25 microns.

227. The method of any one of embodiments 212 to 226, further comprisingsorting the plurality of diatom frustule portions to separate a firstdiatom frustule portion from a second diatom frustule portion, the firstdiatom frustule portion having a greater longest dimension.

228. The method of embodiment 227, wherein the first diatom frustuleportion comprises a plurality of unbroken diatom frustule portions.

229. The method of embodiment 227 or 228, wherein the second diatomfrustule portion comprises a plurality of broken diatom frustuleportions.

230. The method of any one of embodiments 227 to 229, wherein sortingcomprises filtering the plurality of diatom frustule portions.

231. The method of embodiment 230, wherein filtering comprisesdisturbing agglomeration of the plurality of diatom frustule portions.

232. The method of embodiment 231, wherein disturbing agglomeration ofthe plurality of diatom frustule portions comprises stirring.

233. The method of embodiment 231 or 282, wherein disturbingagglomeration of the plurality of diatom frustule portions comprisesshaking.

234. The method of any one of embodiments 231 to 233, wherein disturbingagglomeration of the plurality of diatom frustule portions comprisesbubbling.

235. The method of any one of embodiments 230 to 234, wherein filteringcomprises applying a sieve to the plurality of diatom frustule portions.

236. The method of embodiment 235, wherein the sieve has a mesh sizefrom about 5 microns to about 10 microns.

237. The method of embodiment 235, wherein the sieve has a mesh size ofabout 7 microns.

238. The method of any one of embodiments 212 to 237, further comprisingobtaining a washed diatom frustule portion.

239. The method of embodiment 238, wherein obtaining the washed diatomfrustule portion comprises washing the plurality of diatom frustuleportions with a cleaning solvent after removing at least one of theorganic contaminant and the inorganic contaminant.

240. The method of embodiment 238 or 239, wherein obtaining the washeddiatom frustule portion comprises washing the diatom frustule portionhaving the at least one common characteristic with a cleaning solvent.

241. The method of embodiment 239 or 240, further comprising removingthe cleaning solvent.

242. The method of embodiment 241, wherein removing the cleaning solventcomprises sedimenting the plurality of diatom frustule portions afterremoving the at least one of the organic contaminant and the inorganiccontaminant.

243. The method of embodiment 241 or 242, wherein removing the cleaningsolvent comprises sedimenting the plurality of diatom frustule portionshaving the at least one common characteristic.

244. The method of embodiment 242 or 243, wherein sedimenting comprisescentrifuging.

245. The method of embodiment 244, wherein centrifuging comprisesapplying a centrifuge suitable for large scale processing.

246. The method of embodiment 245, wherein centrifuging comprisesapplying at least one of a disc stack centrifuge, a decanter centrifuge,and a tubular bowl centrifuge.

247. The method of any one of embodiments 240 to 246, wherein at leastone of the dispersing solvent and the cleaning solvent comprises water.

248. The method of any one of embodiments 215 to 247, wherein at leastone of dispersing the plurality of diatom frustule portions in thedispersing solvent and dispersing the plurality of diatom frustuleportions in the surfactant comprises sonicating the plurality of diatomfrustules.

249. The method of any one of embodiments 215 to 248, wherein thesurfactant comprises a cationic surfactant.

250. The method of embodiment 249, wherein the cationic surfactantcomprises at least one of a benzalkonium chloride, a cetrimoniumbromide, a lauryl methyl gluceth-10 hydroxypropyl dimonium chloride, abenzethonium chloride, a benzethonium chloride, a bronidox, admethyldioctadecylammonium chloride, and a tetramethylammoniumhydroxide.

251. The method of any one of embodiments 212 to 250, wherein thesurfactant comprises a non-ionic surfactant.

252. The method of embodiment 251, wherein the non-ionic surfactantcomprises at least one of a cetyl alcohol, a stearyl alcohol, acetostearyl alcohol, an oleyl alcohol, a polyoxyethylene glycol alkylether, an octaethylene glycol monododecyl ether, a glucoside alkylethers, a decyl glucoside, a polyoxyethylene glycol octylphenol ethers,an octylphenol ethoxylate (Triton X-100™), a nonoxynol-9, a glyceryllaurate, a polysorbate, and a poloxamer.

253. The method of any one of embodiments 212 to 252, further comprisingdispersing the plurality of diatom frustules in an additive component.

254. The method of embodiment 253, wherein dispersing the plurality ofdiatom frustules in an additive component is before dispersing theplurality of diatom frustules in the surfactant.

255. The method of embodiment 253, wherein dispersing the plurality ofdiatom frustules in an additive component is after dispersing theplurality of diatom frustules in the surfactant.

256. The method of embodiment 253, wherein dispersing the plurality ofdiatom frustules in an additive component is at least partiallysimultaneous with dispersing the plurality of diatom frustules in thesurfactant.

257. The method of any one of embodiments 253 to 256, wherein theadditive component comprises at least one of a potassium chloride, anammonium chloride, an ammonium hydroxide, and a sodium hydroxide.

258. The method of any one of embodiments 213 to 257, wherein dispersingthe plurality of diatom frustule portions in the dispersing solventcomprises obtaining a dispersion comprising about 1 weight percent toabout 5 weight percent of the plurality of diatom frustule portions.

259. The method of any one of embodiments 214 to 258, wherein removingthe organic contaminant comprises heating the plurality of diatomfrustule portions in the presence of a bleach.

260. The method of embodiment 259, wherein the bleach comprises at leastone of a hydrogen peroxide, and a nitric acid.

261. The method of embodiment 260, wherein heating comprises heating theplurality of diatom frustule portions in a solution comprising an amountof hydrogen peroxide in a range from about 10 volume percent to about 20volume percent.

262. The method of any one of embodiments 259 to 261, wherein heatingcomprises heating the plurality of diatom frustule portions for aduration of about 5 minutes to about 15 minutes.

263. The method of any one of embodiments 214 to 262, wherein removingthe organic contaminant comprises annealing the plurality of diatomfrustule portions.

264. The method of any one of embodiments 214 to 263, wherein removingthe inorganic contaminant comprises combining the plurality of diatomfrustule portions with at least one of a hydrochloric acid and asulfuric acid.

265. The method of embodiment 264, wherein combining comprises mixingthe plurality of diatom frustule portions in a solution comprising about15 volume percent to about 25 volume percent of hydrochloric acid.

266. The method of embodiment 265, wherein the mixing is for a durationof about 20 minutes to about 40 minutes.

267. A method of extracting a diatom frustule portion, the methodcomprising:

-   -   dispersing a plurality of diatom frustule portions with a        surfactant, the surfactant reducing an agglomeration of the        plurality of diatom frustule portions.

268. The method of embodiment 267, further comprising extracting aplurality of diatom frustule portions having at least one commoncharacteristic using a disc stack centrifuge.

269. The method of embodiment 267 or 268, further comprising dispersingthe plurality of diatom frustule portions in a dispersing solvent.

270. The method of any one of embodiments 267 to 269, further comprisingremoving at least one of an organic contaminant and an inorganiccontaminant.

271. The method of any one of embodiments 267 to 270, wherein the atleast one common characteristic comprises at least one of a dimension, ashape, a material, and a degree of brokenness.

272. The method of embodiment 271, wherein the dimension comprises atleast one of a length and a diameter.

273. The method of any one of embodiments 267 to 272, wherein a solidmixture comprises the plurality of diatom frustule portions.

274. The method of embodiment 273, further comprising reducing aparticle dimension of the solid mixture.

275. The method of embodiment 274, wherein reducing the particledimension of the solid mixture is before dispersing the plurality ofdiatom frustule portions in the dispersing solvent.

276. The method of embodiment 274 or 275, wherein reducing the particledimension comprises grinding the solid mixture.

277. The method of embodiment 276, wherein grinding the solid mixturecomprises applying to the solid mixture at least one of a mortar and apestle, a jar mill, and a rock crusher.

278. The method of any one of embodiments 273 to 277, further comprisingextracting a component of the solid mixture having a longest componentdimension that is greater than a longest frustule portion dimension ofthe plurality of diatom frustule portions.

279. The method of embodiment 278, wherein extracting the component ofthe solid mixture comprises sieving the solid mixture.

280. The method of embodiment 279, wherein sieving the solid mixturecomprises processing the solid mixture with a sieve having a mesh sizefrom about 15 microns to about 25 microns.

281. The method of embodiment 279, wherein sieving the solid mixturecomprises processing the solid mixture with a sieve having a mesh sizefrom about 10 microns to about 25 microns.

282. The method of any one of embodiments 267 to 281, further comprisingsorting the plurality of diatom frustule portions to separate a firstdiatom frustule portion from a second diatom frustule portion, the firstdiatom frustule portion having a greater longest dimension.

283. The method of embodiment 282, wherein the first diatom frustuleportion comprises a plurality of unbroken diatom frustule portions.

284. The method of embodiment 282 or 283, wherein the second diatomfrustule portion comprises a plurality of broken diatom frustuleportions.

285. The method of any one of embodiments 282 to 284, wherein sortingcomprises filtering the plurality of diatom frustule portions.

286. The method of embodiment 285, wherein filtering comprisesdisturbing agglomeration of the plurality of diatom frustule portions.

287. The method of embodiment 286, wherein disturbing agglomeration ofthe plurality of diatom frustule portions comprises stirring.

288. The method of embodiment 286 or 287, wherein disturbingagglomeration of the plurality of diatom frustule portions comprisesshaking.

289. The method of any one of embodiments 286 to 288, wherein disturbingagglomeration of the plurality of diatom frustule portions comprisesbubbling.

290. The method of any one of embodiments 285 to 289, wherein filteringcomprises applying a sieve to the plurality of diatom frustule portions.

291. The method of embodiment 290, wherein the sieve has a mesh sizefrom about 5 microns to about 10 microns.

292. The method of embodiment 290, wherein the sieve has a mesh size ofabout 7 microns.

293. The method of any one of embodiments 267 to 292, further comprisingobtaining a washed diatom frustule portion.

294. The method of embodiment 293, wherein obtaining the washed diatomfrustule portion comprises washing the plurality of diatom frustuleportions with a cleaning solvent after removing the at least one of theorganic contaminant and the inorganic contaminant.

295. The method of embodiment 293 or 294 wherein obtaining the washeddiatom frustule portion comprises washing the diatom frustule portionhaving the at least one common characteristic with a cleaning solvent.

296. The method of embodiment 294 or 295, further comprising removingthe cleaning solvent.

297. The method of embodiment 296, wherein removing the cleaning solventcomprises sedimenting the plurality of diatom frustule portions afterremoving the at least one of the organic contaminant and the inorganiccontaminant.

298. The method of embodiment 296 or 297, wherein removing the cleaningsolvent comprises sedimenting the plurality of diatom frustule portionshaving the at least one common characteristic.

299. The method of embodiment 297 or 298, wherein sedimenting comprisescentrifuging.

300. The method of embodiment 299, wherein centrifuging comprisesapplying a centrifuge suitable for large scale processing.

301. The method of embodiment 300, wherein centrifuging comprisesapplying at least one of a disc stack centrifuge, a decanter centrifuge,and a tubular bowl centrifuge.

302. The method of any one of embodiments 295 to 301, wherein at leastone of the dispersing solvent and the cleaning solvent comprises water.

303. The method of any one of embodiments 269 to 302, wherein at leastone of dispersing the plurality of diatom frustule portions in thedispersing solvent and dispersing the plurality of diatom frustuleportions in the surfactant comprises sonicating the plurality of diatomfrustules.

304. The method of any one of embodiments 267 to 303, wherein thesurfactant comprises a cationic surfactant.

305. The method of embodiment 304, wherein the cationic surfactantcomprises at least one of a benzalkonium chloride, a cetrimoniumbromide, a lauryl methyl gluceth-10 hydroxypropyl dimonium chloride, abenzethonium chloride, a benzethonium chloride, a bronidox, admethyldioctadecylammonium chloride, and a tetramethylammoniumhydroxide.

306. The method of any one of embodiments 267 to 305, wherein thesurfactant comprises a non-ionic surfactant.

307. The method of embodiment 306, wherein the non-ionic surfactantcomprises at least one of a cetyl alcohol, a stearyl alcohol, acetostearyl alcohol, an oleyl alcohol, a polyoxyethylene glycol alkylether, an octaethylene glycol monododecyl ether, a glucoside alkylethers, a decyl glucoside, a polyoxyethylene glycol octylphenol ethers,an octylphenol ethoxylate (Triton X-100™), a nonoxynol-9, a glyceryllaurate, a polysorbate, and a poloxamer.

308. The method of any one of embodiments 267 to 307, further comprisingdispersing the plurality of diatom frustules in an additive component.

309. The method of embodiment 308, wherein dispersing the plurality ofdiatom frustules in an additive component is before dispersing theplurality of diatom frustules in the surfactant.

310. The method of embodiment 308, wherein dispersing the plurality ofdiatom frustules in an additive component is after dispersing theplurality of diatom frustules in the surfactant.

311. The method of embodiment 308, wherein dispersing the plurality ofdiatom frustules in an additive component is at least partiallysimultaneous with dispersing the plurality of diatom frustules in thesurfactant.

312. The method of any one of embodiments 308 to 311, wherein theadditive component comprises at least one of a potassium chloride, anammonium chloride, an ammonium hydroxide, and a sodium hydroxide.

313. The method of any one of embodiments 269 to 312, wherein dispersingthe plurality of diatom frustule portions in the dispersing solventcomprises obtaining a dispersion comprising about 1 weight percent toabout 5 weight percent of the plurality of diatom frustule portions.

314. The method of any one of embodiments 270 to 313, wherein removingthe organic contaminant comprises heating the plurality of diatomfrustule portions in the presence of a bleach.

315. The method of embodiment 314, wherein the bleach comprises at leastone of a hydrogen peroxide, and a nitric acid.

316. The method of embodiment 315, wherein heating comprises heating theplurality of diatom frustule portions in a solution comprising an amountof hydrogen peroxide in a range from about 10 volume percent to about 20volume percent.

317. The method of any one of embodiments 314 to 316, wherein heatingcomprises heating the plurality of diatom frustule portions for aduration of about 5 minutes to about 15 minutes.

318. The method of any one of embodiments 270 to 317, wherein removingthe organic contaminant comprises annealing the plurality of diatomfrustule portions.

319. The method of any one of embodiments 270 to 218, wherein removingthe inorganic contaminant comprises combining the plurality of diatomfrustule portions with at least one of a hydrochloric acid and asulfuric acid.

320. The method of embodiment 319, wherein combining comprises mixingthe plurality of diatom frustule portions in a solution comprising about15 volume percent to about 25 volume percent of hydrochloric acid.

321. The method of embodiment 320, wherein the mixing is for a durationof about 20 minutes to about 40 minutes.

322. A method of forming silver nanostructures on a diatom frustuleportion, the method comprising:

-   -   forming a silver seed layer on a surface of the diatom frustule        portion; and    -   forming a nanostructure on the seed layer.

323. The method of embodiment 322, wherein the nanostructures comprisesat least one of a coating, a nanowire, a nanoplate, a dense array ofnanoparticles, a nanobelt, and a nanodisk.

324. The method of embodiment 322 or 323, wherein the nanostructurescomprises silver.

325. The method of any one of embodiment 322 to 324, wherein forming thesilver seed layer comprises applying a cyclic heating regimen to a firstsilver contributing component and the diatom frustule portion.

326. The method of embodiment 325, wherein applying the cyclic heatingregimen comprises applying a cyclic microwave power.

327. The method of embodiment 326, wherein applying the cyclic microwavepower comprises alternating a microwave power between about 100 Watt and500 Watt.

328. The method of embodiment 327, wherein alternating comprisesalternating the microwave power every minute.

329. The method of embodiment 327 or 328, wherein alternating comprisesalternating the microwave power for a duration of about 30 minutes.

330. The method of embodiment 327 or 328, wherein alternating comprisesalternating the microwave power for a duration of about 20 minutes toabout 40 minutes.

331. The method of any one of embodiments 322 to 330, wherein formingthe silver seed layer comprises combining the diatom frustule portionwith a seed layer solution.

332. The method of embodiment 331, wherein the seed layer solutioncomprises the first silver contributing component and a seed layerreducing agent.

333. The method of embodiment 332, wherein the seed layer reducing agentis a seed layer solvent.

334. The method of embodiment 333, wherein the seed layer reducing agentand the seed layer solvent comprises a polyethylene glycol.

335. The method of embodiment 331, wherein the seed layer solutioncomprises the first silver contributing component, a seed layer reducingagent and a seed layer solvent.

336. The method of any one of embodiments 331 to 335, wherein formingthe silver seed layer further comprises mixing the diatom frustuleportion with the seed layer solution.

337. The method of embodiment 336, wherein mixing comprisesultrasonicating.

338. The method of embodiment 337, wherein the seed layer reducing agentcomprises a N,N-Dimethylformamide, the first silver contributingcomponent comprises a silver nitrate, and the seed layer solventcomprises at least one of a water and a polyvinylpyrrolidone.

339. The method of any one of embodiments 322 to 338, wherein formingthe nanostructure comprises combining the diatom frustule portion with ananostructure forming reducing agent.

340. The method of embodiment 339, wherein forming the nanostructurefurther comprises heating the diatom frustule portion after combiningthe diatom frustule portion with the nanostructure forming reducingagent.

341. The method of embodiment 340, wherein heating comprises heating toa temperature of about 120° C. to about 160° C.

342. The method of embodiment 340 or 341, wherein forming thenanostructure further comprises titrating the diatom frustule portionwith a titration solution comprising a nanostructure forming solvent anda second silver contributing component.

343. The method of embodiment 342, wherein forming the nanostructurefurther comprises mixing after titrating the diatom frustule portionwith the titration solution.

344. The method of any one of embodiments 339 to 343, wherein at leastone of the seed layer reducing agent and the nanostructure formingreducing agent comprises at least one of a hydrazine, a formaldehyde, aglucose, sodium tartrate, an oxalic acid, a formic acid, an ascorbicacid, and an ethylene glycol.

345. The method of any one of embodiments 342 to 344, wherein at leastone of the first silver contributing component and the second silvercontributing component comprises at least one of a silver salt and asilver oxide.

346. The method of embodiment 345, wherein the silver salt comprises atleast one of a silver nitrate and an ammoniacal silver nitrate, a silverchloride (AgCl), a silver cyanide (AgCN), a silver tetrafluoroborate, asilver hexafluorophosphate, and a silver ethylsulphate.

347. The method of any one of embodiments 322 to 346, wherein formingthe nanostructure is in an ambient to reduce oxide formation.

348. The method of embodiment 347, wherein the ambient comprises anargon atmosphere.

349. The method of any one of embodiments 342 to 348, wherein at leastone of the seed layer solvent and the nanostructure forming solventcomprises at least one of a proplyene glycol, a water, a methanol, anethanol, a 1-propanol, a 2-propanol a 1-methoxy-2-propanol, a 1-butanol,a 2-butanol a 1-pentanol, a 2-pentanol, a 3-pentanol, a 1-hexanol, a2-hexanol, a 3-hexanol, an octanol, a 1-octanol, a 2-octanol, a3-octanol, a tetrahydrofurfuryl alcohol (THFA), a cyclohexanol, acyclopentanol, a terpineol, a butyl lactone; a methyl ethyl ether, adiethyl ether, an ethyl propyl ether, a polyethers, a diketones, acyclohexanone, a cyclopentanone, a cycloheptanone, a cyclooctanone, anacetone, a benzophenone, an acetylacetone, an acetophenone, acyclopropanone, an isophorone, a methyl ethyl ketone, an ethyl acetate,a dimethyl adipate, a proplyene glycol monomethyl ether acetate, adimethyl glutarate, a dimethyl succinate, a glycerin acetate, acarboxylates, a propylene carbonate, a glycerin, a diol, a triol, atetraol, a pentaol, an ethylene glycol, a diethylene glycol, apolyethylene glycol, a propylene glycol, a dipropylene glycol, a glycolether, a glycol ether acetate, a 1,4-butanediol, a 1,2-butanediol, a2,3-butanediol, a 1,3-propanediol, a 1,4-butanediol, a 1,5-pentanediol,a 1,8-octanediol, a 1,2-propanediol, a 1,3-butanediol, a1,2-pentanediol, an etohexadiol, a p-menthane-3,8-diol, a2-methyl-2,4-pentanediol, a tetramethyl urea, a n-methylpyrrolidone, anacetonitrile, a tetrahydrofuran (THF), a dimethyl formamide (DMF), aN-methyl formamide (NMF), a dimethyl sulfoxide (DMSO), a thionylchloride and a sulfuryl chloride.

350. The method of any one of embodiments 322 to 349, wherein the diatomfrustule portion comprises a broken diatom frustule portion.

351. The method of any one of embodiments 322 to 349, wherein the diatomfrustule portion comprises an unbroken diatom frustule portion.

352. The method of any one of embodiments 322 to 351, wherein the diatomfrustule portion is obtained through a diatom frustule portionseparation process.

353. The method of embodiment 352, wherein the process comprises atleast one of using a surfactant to reduce an agglomeration of aplurality of diatom frustule portions and using a disc stack centrifuge.

354. A method of forming zinc-oxide nanostructures on a diatom frustuleportion, the method comprising:

-   -   forming a zinc-oxide seed layer on a surface of the diatom        frustule portion; and    -   forming a nanostructure on the zinc-oxide seed layer.

355. The method of embodiment 354, wherein the nanostructure comprisesat least one of a nanowire, a nanoplate, a dense array of nanoparticles,a nanobelt, and a nanodisk.

356. The method of embodiment 354 or 355, wherein the nanostructurescomprises zinc-oxide.

357. The method of any one of embodiments 354 to 356, wherein formingthe zinc-oxide seed layer comprises heating a first zinc contributingcomponent and the diatom frustule portion.

358. The method of embodiment 357, wherein heating the first zinccontributing component and the diatom frustule portion comprises heatingto a temperature in a range from about 175° C. to about 225° C.

359. The method of any one of embodiments 354 to 358, wherein formingthe nanostructure comprises applying a heating regimen to the diatomfrustule portion having the zinc-oxide seed layer in the presence of ananostructure forming solution comprising a second zinc contributingcomponent.

360. The method of embodiment 359, wherein the heating regimen comprisesheating to a nanostructure forming temperature.

361. The method of embodiment 360, wherein the nanostructure formingtemperature is from about 80° C. to about 100° C.

362. The method of embodiment 360 or 361, wherein the heating is for aduration of about one to about three hours.

363. The method of any one of embodiments 359 to 362, wherein theheating regimen comprises applying a cyclic heating routine.

364. The method of embodiment 363, wherein the cyclic heating routinecomprises applying a microwave heating to the diatom frustule portionhaving the zinc-oxide seed layer for a heating duration and then turningthe microwaving heating off for a cooling duration, for a total cyclicheating duration.

365. The method of embodiment 364, wherein the heating duration is about1 minute to about 5 minutes.

366. The method of embodiment 364 or 365, wherein the cooling durationis about 30 seconds to about 5 minutes.

367. The method of any one of embodiments 364 to 366, wherein the totalcyclic heating duration is about 5 minutes to about 20 minutes.

368. The method of any one of embodiments 364 to 367, wherein applyingthe microwave heating comprises applying about 480 Watt to about 520Watt of microwave power.

369. The method of any one of embodiments 364 to 367, wherein applyingthe microwave heating comprises applying about 80 Watt to about 120 Wattof microwave power.

370. The method of any one of embodiments 359 to 369, wherein at leastone of the first zinc contributing component and the second zinccontributing component comprise at least one of a zinc acetate, a zincacetate hydrate, a zinc nitrate, a zinc nitrate hexahydrate, a zincchloride, a zinc sulfate, and a sodium zincate.

371. The method of any one of embodiments 359 to 370, wherein thenanostructure forming solution comprises a base.

372. The method of embodiment 371, wherein the base comprises at leastone of a sodium hydroxide, an ammonium hydroxide, potassium hydroxide, ateramethylammonium hydroxide, a lithium hydroxide, ahexamethylenetetramine, an ammonia solution, a sodium carbonate, and aethylenediamine.

373. The method of any one of embodiments 354 to 372, wherein formingthe nanostructure further comprises adding an additive component.

374. The method of embodiment 373, wherein the additive componentcomprises at least one of a tributylamine, a triethylamine, atriethanolamine, a diisopropylamine, an ammonium phosphate, a1,6-hexadianol, a triethyldiethylnol, an isopropylamine, acyclohexylamine, a n-butylamine, an ammonium chloride, ahexamethylenetetramine, an ethylene glycol, an ethanoamine, apolyvinylalcohol, a polyethylene glycol, a sodium dodecyl sulphate, acetyltrimethyl ammonium bromide, and a carbamide.

375. The method of any one of embodiments 359 to 374, wherein at leastone of the nanostructure forming solution and a zinc-oxide seed layerforming solution comprises a solvent, the solvent comprising at leastone of a proplyene glycol, a water, a methanol, an ethanol, a1-propanol, a 2-propanol a 1-methoxy-2-propanol, a 1-butanol, a2-butanol a 1-pentanol, a 2-pentanol, a 3-pentanol, a 1-hexanol, a2-hexanol, a 3-hexanol, an octanol, a 1-octanol, a 2-octanol, a3-octanol, a tetrahydrofurfuryl alcohol (THFA), a cyclohexanol, acyclopentanol, a terpineol, a butyl lactone; a methyl ethyl ether, adiethyl ether, an ethyl propyl ether, a polyethers, a diketones, acyclohexanone, a cyclopentanone, a cycloheptanone, a cyclooctanone, anacetone, a benzophenone, an acetylacetone, an acetophenone, acyclopropanone, an isophorone, a methyl ethyl ketone, an ethyl acetate,a dimethyl adipate, a proplyene glycol monomethyl ether acetate, adimethyl glutarate, a dimethyl succinate, a glycerin acetate, acarboxylates, a propylene carbonate, a glycerin, a diol, a triol, atetraol, a pentaol, an ethylene glycol, a diethylene glycol, apolyethylene glycol, a propylene glycol, a dipropylene glycol, a glycolether, a glycol ether acetate, a 1,4-butanediol, a 1,2-butanediol, a2,3-butanediol, a 1,3-propanediol, a 1,4-butanediol, a 1,5-pentanediol,a 1,8-octanediol, a 1,2-propanediol, a 1,3-butanediol, a1,2-pentanediol, an etohexadiol, a p-menthane-3,8-diol, a2-methyl-2,4-pentanediol, a tetramethyl urea, a n-methylpyrrolidone, anacetonitrile, a tetrahydrofuran (THF), a dimethyl formamide (DMF), aN-methyl formamide (NMF), a dimethyl sulfoxide (DMSO), a thionylchloride and a sulfuryl chloride.

376. The method of any one of embodiments 354 to 375, wherein the diatomfrustule portion comprises a broken diatom frustule portion.

377. The method of any one of embodiments 354 to 375, wherein the diatomfrustule portion comprises an unbroken diatom frustule portion.

378. The method of any one of embodiments 354 to 375, wherein the diatomfrustule portion is obtained through a diatom frustule portionseparation process.

379. The method of embodiment 378, wherein the process comprises atleast one of using a surfactant to reduce an agglomeration of aplurality of diatom frustule portions and using a disc stack centrifuge.

380. A method of forming carbon nanostructures on a diatom frustuleportion, the method comprising:

-   -   forming a metal seed layer on a surface of the diatom frustule        portion; and    -   forming a carbon nanostructure on the seed layer.

381. The method of embodiment 380, wherein the carbon nanostructurecomprises a carbon nanotube.

382. The method of embodiment 381, wherein the carbon nanotube compriseat least one of a single-walled carbon nanotube and a multi-walledcarbon nanotube.

383. The method of any one of embodiments 380 to 382, wherein formingthe metal seed layer comprises spray coating the surface of the diatomfrustule portion.

384. The method of any one of embodiments 380 to 383, wherein formingthe metal seed layer comprises introducing the surface of the diatomfrustule portion to at least one of a liquid comprising the metal, a gascomprising the metal and the solid comprising a metal.

385. The method of any one of embodiments 380 to 384, wherein formingthe carbon nanostructure comprises using chemical vapor deposition(CVD).

386. The method of any one of embodiments 380 to 385, wherein formingthe carbon nanostructure comprises exposing the diatom frustule portionto a nanostructure forming reducing gas after exposing the diatomfrustule portion to a nanostructure forming carbon gas.

387. The method of any one of embodiments 380 to 385, wherein formingthe carbon nanostructure comprises exposing the diatom frustule portionto a nanostructure forming reducing gas before exposing the diatomfrustule portion to a nanostructure forming carbon gas.

388. The method of any one of embodiments 380 to 385, wherein formingthe carbon nanostructure comprises exposing the diatom frustule portionto a nanostructure forming gas mixture comprising a nanostructureforming reducing gas and a nanostructure forming carbon gas.

389. The method of embodiment 388, wherein the nanostructure forming gasmixture further comprises a neutral gas.

390. The method of embodiment 389, wherein the neutral gas comprisesargon.

391. The method of any one of embodiments 380 to 390, wherein the metalcomprises at least one of a nickel, an iron, a cobalt, acobalt-molibdenium bimetallic, a copper, a gold, a silver, a platinum, apalladium, a manganese, an aluminum, a magnesium, a chromium, anantimony, an aluminum-iron-molybdenum (Al/Fe/Mo), an iron pentacarbonyl(Fe(CO)₅)), an iron (III) nitrate hexahydrate ((Fe(NO₃)₃.6H₂O), acolbalt (II) chloride hexahydrate (CoCl₂.6H₂O), an ammonium molybdatetetrahydrate ((NH₄)₆Mo₇O₂₄.4H₂O), a molybdenum (VI) dichloride dioxideMoO₂Cl₂, and an alumina nanopowder.

392. The method of any one of embodiments 286 to 391, wherein thenanostructure forming reducing gas comprises at least one of an ammonia,a nitrogen, and a hydrogen.

393. The method of any one of embodiments 286 to 392, wherein thenanostructure forming carbon gas comprises at least one of an acetylene,an ethylene, an ethanol, a methane, a carbon oxide, and a benzene.

394. The method of any one of embodiments 380 to 393, wherein formingthe metal seed layer comprises forming a silver seed layer.

395. The method of embodiment 394, wherein forming the silver seed layercomprises forming a silver nanostructure on the surface of the diatomfrustule portion.

396. The method of any one of embodiments 380 to 395, wherein the diatomfrustule portion comprises a broken diatom frustule portion.

397. The method of any one of embodiments 380 to 395, wherein the diatomfrustule portion comprises an unbroken diatom frustule portion.

398. The method of any one of embodiments 380 to 397, wherein the diatomfrustule portion is obtained through a diatom frustule portionseparation process.

399. The method of embodiment 398, wherein the process comprises atleast one of using a surfactant to reduce an agglomeration of aplurality of diatom frustule portions and using a disc stack centrifuge.

400. A method of fabricating a silver ink, the method comprising:

-   -   combining an ultraviolet light sensitive component and a        plurality of diatom frustule portions having a silver        nanostructure on a surface of the plurality of diatom frustule        portions, the surface comprising a plurality of perforations.

401. The method of embodiment 400, further comprising forming a silverseed layer on the surface of the plurality of diatom frustule portions.

402. The method of embodiment 400 or 401, further comprising forming thesilver nanostructure on the seed layer.

403. The method of any one of embodiments 400 to 402, wherein theplurality of diatom frustule portions comprises a plurality of brokendiatom frustule portions.

404. The method of any one of embodiments 400 to 403, wherein theplurality of diatom frustule portions comprises a plurality of diatomfrustule flakes.

405. The method of any one of embodiments 400 to 404, wherein the silverink is depositable in a layer having a thickness of about 5 microns toabout 15 microns after curing.

406. The method of any one of embodiments 400 to 405, wherein at leastone of the plurality of perforations comprises a diameter of about 250nanometers to about 350 nanometers.

407. The method of any one of embodiments 400 to 406, wherein the silvernanostructure comprises a thickness of about 10 nanometers to about 500nanometers.

408. The method of any one of embodiments 400 to 407, wherein the silverink comprises an amount of diatom frustules within a range of about 50weight percent to about 80 weight percent.

409. The method of any one of embodiments 401 to 408, wherein formingthe silver seed layer comprises forming the silver seed layer on asurface within the plurality of perforations to form a plurality ofsilver seed plated perforations.

410. The method of any one of embodiments 401 to 409, wherein formingthe silver seed layer comprises forming the silver seed layer onsubstantially all surfaces of the plurality of diatom frustule portions.

411. The method of any one of embodiments 402 to 410, wherein formingthe silver nanostructure comprises forming the silver nanostructure on asurface within the plurality of perforations to form a plurality ofsilver nanostructure plated perforations.

412. The method of any one of embodiments 402 to 411, wherein formingthe silver nanostructure comprises forming the silver nanostructure onsubstantially all surfaces of the plurality of diatom frustule portions.

413. The method of any one of embodiments 400 to 412, wherein theultraviolet light sensitive component is sensitive to an opticalradiation having a wavelength shorter than a dimension of the pluralityof perforations.

414. The method of any one of embodiments 411 to 413, wherein theultraviolet light sensitive component is sensitive to an opticalradiation having a wavelength shorter than a dimension of at least oneof the plurality of silver seed plated perforations and the plurality ofsilver nanostructure plated perforations.

415. The method of any one of embodiments 400 to 414, wherein combiningthe plurality of diatom frustule portions with the ultraviolet lightsensitive component comprises combining the plurality of diatom frustuleportions with a photoinitiation synergist agent.

416. The method of embodiment 415, wherein the photoinitiation synergistagent comprises at least one of an ethoxylated hexanediol acrylate, apropoxylated hexanediol acrylate, an ethoxylated trimethylpropanetriacrylate, a triallyl cyanurate and an acrylated amine.

417. The method of any one of embodiments 400 to 416, wherein combiningthe plurality of diatom frustule portions with the ultraviolet lightsensitive component comprises combining the plurality of diatom frustuleportions with a photoinitiator agent.

418. The method of embodiment 417, wherein the photoinitiator agentcomprises at least one of a2-methyl-1-(4-methylthio)phenyl-2-morpholinyl-1-propanon and anisopropyl thioxothanone.

419. The method of any one of embodiments 400 to 418, wherein combiningthe plurality of diatom frustule portions with the ultraviolet lightsensitive component comprises combining the plurality of diatom frustuleportions with a polar vinyl monomer.

420. The method of embodiment 419, wherein the polar vinyl monomercomprises at least one of a n-vinyl-pyrrolidone and an-vinylcaprolactam.

421. The method of any one of embodiments 400 to 420, further comprisingcombining the plurality of diatom frustule portions with a rheologymodifying agent.

422. The method of any one of embodiments 400 to 421, further comprisingcombining the plurality of diatom frustule portions with a crosslinkingagent.

423. The method of any one of embodiments 400 to 422, further comprisingcombining the plurality of diatom frustule portions with a flow andlevel agent.

424. The method of any one of embodiments 400 to 423, further comprisingcombining the plurality of diatom frustule portions with at least one ofan adhesion promoting agent, a wetting agent, and a viscosity reducingagent.

425. The method of any one of embodiments 400 to 424, wherein the silvernanostructure comprises at least one of a coating, a nanowire, ananoplate, a dense array of nanoparticles, a nanobelt, and a nanodisk.

426. The method of any one of embodiment 401 to 425, wherein forming thesilver seed layer comprises applying a cyclic heating regimen to a firstsilver contributing component and the plurality of diatom frustuleportions.

427. The method of any one of embodiments 401 to 426, wherein formingthe silver seed layer comprises combining the diatom frustule portionwith a seed layer solution.

428. The method of embodiment 427, wherein the seed layer solutioncomprises the first silver contributing component and a seed layerreducing agent.

429. The method of any one of embodiments 402 to 428, wherein formingthe silver nanostructure comprises combining the diatom frustule portionwith a nanostructure forming reducing agent.

430. The method of embodiment 429, wherein forming the silvernanostructure further comprises heating the diatom frustule portionafter combining the diatom frustule portion with the nanostructureforming reducing agent.

431. The method of any one of embodiments 402 to 430, wherein formingthe silver nanostructure further comprises titrating the diatom frustuleportion with a titration solution comprising a nanostructure formingsolvent and a second silver contributing component.

432. The method of any one of embodiments 400 to 431, wherein theplurality of diatom frustule portions are obtained through a diatomfrustule portion separation process.

433. The method of embodiment 432, wherein the process comprises atleast one of using a surfactant to reduce an agglomeration of aplurality of diatom frustule portions and using a disc stack centrifuge.

434. A conductive silver ink comprising:

-   -   an ultraviolet light sensitive component; and    -   a plurality of diatom frustule portions having a silver        nanostructure on a surface of the plurality of diatom frustule        portions, the surface comprising a plurality of perforations.

435. The conductive silver ink of embodiment 434, wherein the pluralityof diatom frustule portions comprises a plurality of broken diatomfrustule portion.

436. The conductive silver ink of embodiment 434 or 435, wherein theplurality of diatom frustule portions comprises a plurality of diatomfrustule flakes.

437. The conductive silver ink of any one of embodiments 434 to 436,wherein the silver ink is depositable in a layer having a thickness ofabout 5 microns to about 15 microns after curing.

438. The conductive silver ink of any one of embodiments 434 to 437,wherein at least one of the plurality of perforations comprises adiameter of about 250 nanometers to about 350 nanometers.

439. The conductive silver ink of any one of embodiments 434 to 438,wherein the silver nanostructure comprises a thickness of about 10nanometers to about 500 nanometers.

440. The conductive silver ink of any one of embodiments 434 to 439,wherein the silver ink comprises an amount of diatom frustules within arange of about 50 weight percent to about 80 weight percent.

441. The conductive silver ink of any one of embodiments 434 to 440,wherein at least one of the plurality of perforations comprises asurface having a silver nanostructure.

442. The conductive silver ink of any one of embodiments 434 to 441,wherein at least one of the plurality of perforations comprises asurface having a silver seed layer.

443. The conductive silver ink of any one of embodiments 434 to 442,wherein substantially all surfaces of the plurality of diatom frustuleportions comprises a silver nanostructure.

444. The conductive silver ink of any one of embodiments 434 to 443,wherein the ultraviolet light sensitive component is sensitive to anoptical radiation having a wavelength shorter than a dimension of theplurality of perforations.

445. The conductive silver ink of any one of embodiments 434 to 444,wherein the conductive silver ink is curable by an ultravioletradiation.

446. The conductive silver ink of embodiment 445, wherein the conductivesilver ink is curable when deposited in a layer having a thickness ofabout 5 microns to about 15 microns after curing.

447. The conductive silver ink of embodiment 445 or 446, wherein theplurality of perforations has a dimension configured to allow theultraviolet radiation to pass through the plurality of diatom frustuleportions.

448. The conductive silver ink of any one of embodiments 434 to 447,wherein the conductive silver ink is thermally curable.

449. The conductive silver ink of any one of embodiments 434 to 448,wherein the ultraviolet light sensitive component comprises aphotoinitiation synergist agent.

450. The conductive silver ink of embodiment 449, wherein thephotoinitiation synergist agent comprises at least one of an ethoxylatedhexanediol acrylate, a propoxylated hexanediol acrylate, an ethoxylatedtrimethylpropane triacrylate, a triallyl cyanurate and an acrylatedamine.

451. The conductive silver ink of any one of embodiments 434 to 450,wherein the ultraviolet light sensitive component comprises aphotoinitiator agent.

452. The conductive silver ink of embodiment 451, wherein thephotoinitiator agent comprises at least one of a2-methyl-1-(4-methylthio)phenyl-2-morpholinyl-1-propanon and anisopropyl thioxothanone.

453. The conductive silver ink of any one of embodiments 434 to 452,wherein the ultraviolet light sensitive component comprises a polarvinyl monomer.

454. The conductive silver ink of embodiment 453, wherein the polarvinyl monomer comprises at least one of a n-vinyl-pyrrolidone and an-vinylcaprolactam.

455. The conductive silver ink of any one of embodiments 434 to 454,further comprising at least one of a rheology modifying agent, acrosslinking agent, a flow and level agent, an adhesion promoting agent,a wetting agent, and a viscosity reducing agent.

456. The conductive silver ink of any one of embodiments 434 to 455,wherein the silver nanostructure comprises at least one of a coating, ananowire, a nanoplate, a dense array of nanoparticles, a nanobelt, and ananodisk.

457. A method of fabricating a silver film, the method comprising:

-   -   curing a mixture comprising an ultraviolet light sensitive        component and a plurality of diatom frustule portions having a        silver nanostructure on a surface of the plurality of diatom        frustule portions, the surface comprising a plurality of        perforations.

458. The method of embodiment 457, further comprising forming a silverseed layer on the surface of the plurality of diatom frustule portions.

459. The method of embodiment 457 or 458, further comprising forming thesilver nanostructure on the seed layer.

460. The method of any one of embodiments 457 to 459, further comprisingcombining the plurality of diatom frustule portions with the ultravioletlight sensitive component to form a silver ink.

461. The method of any one of embodiments 457 to 460, wherein theplurality of diatom frustule portions comprises a plurality of brokendiatom frustule portions.

462. The method of any one of embodiments 457 to 461, wherein theplurality of diatom frustule portions comprises a plurality of diatomfrustule flakes.

463. The method of any one of embodiments 460 to 462, wherein the silverink is depositable in a layer having a thickness of about 5 microns toabout 15 microns after curing.

464. The method of any one of embodiments 457 to 463, wherein at leastone of the plurality of perforations comprises a diameter of about 250nanometers to about 350 nanometers.

465. The method of any one of embodiments 457 to 464, wherein the silvernanostructure comprises a thickness of about 10 nanometers to about 500nanometers.

466. The method of any one of embodiments 460 to 465, wherein the silverink comprises an amount of diatom frustules within a range of about 50weight percent to about 80 weight percent.

467. The method of any one of embodiments 458 to 466, wherein formingthe silver seed layer comprises forming the silver seed layer on asurface within the plurality of perforations to form a plurality ofsilver seed plated perforations.

468. The method of any one of embodiments 458 to 467, wherein formingthe silver seed layer comprises forming the silver seed layer onsubstantially all surfaces of the plurality of diatom frustule portions.

469. The method of any one of embodiments 459 to 468, wherein formingthe silver nanostructure comprises forming the silver nanostructure on asurface within the plurality of perforations to form a plurality ofsilver nanostructure plated perforations.

470. The method of any one of embodiments 459 to 469, wherein formingthe silver nanostructure comprises forming the silver nanostructure onsubstantially all surfaces of the plurality of diatom frustule portions.

471. The method of any one of embodiments 457 to 470, wherein curing themixture comprises exposing the mixture to an ultraviolet light having awavelength shorter than a dimension of the plurality of perforations.

472. The method of any one of embodiments 469 to 471, wherein curing themixture comprises exposing the mixture to an ultraviolet light having awavelength shorter than a dimension of at least one of the plurality ofsilver seed plated perforations and the plurality of silver nanostructure plated perforations.

473. The method of any one of embodiments 457 to 472, wherein curing themixture comprises thermally curing the mixture.

474. The method of any one of embodiments 457 to 473, wherein theultraviolet light sensitive component is sensitive to an opticalradiation having a wavelength shorter than a dimension of the pluralityof perforations.

475. The method of any one of embodiments 469 to 474, wherein theultraviolet light sensitive component is sensitive to an opticalradiation having a wavelength shorter than a dimension of at least oneof the plurality of silver seed plated perforations and the plurality ofsilver nanostructure plated perforations.

476. The method of any one of embodiments 460 to 475, wherein combiningthe plurality of diatom frustule portions with the ultraviolet lightsensitive component comprises combining the plurality of diatom frustuleportions with a photoinitiation synergist agent.

477. The method of embodiment 476, wherein the photoinitiation synergistagent comprises at least one of an ethoxylated hexanediol acrylate, apropoxylated hexanediol acrylate, an ethoxylated trimethylpropanetriacrylate, a triallyl cyanurate and an acrylated amine.

478. The method of any one of embodiments 460 to 477, wherein combiningthe plurality of diatom frustule portions with the ultraviolet lightsensitive component comprises combining the plurality of diatom frustuleportions with a photoinitiator agent.

479. The method of embodiment 478, wherein the photoinitiator agentcomprises at least one of a2-methyl-1-(4-methylthio)phenyl-2-morpholinyl-1-propanon and anisopropyl thioxothanone.

480. The method of any one of embodiments 460 to 479, wherein combiningthe plurality of diatom frustule portions with the ultraviolet lightsensitive component comprises combining the plurality of diatom frustuleportions with a polar vinyl monomer.

481. The method of embodiment 480, wherein the polar vinyl monomercomprises at least one of a n-vinyl-pyrrolidone and an-vinylcaprolactam.

482. The method of any one of embodiments 457 to 481, further comprisingcombining the plurality of diatom frustule portions with a rheologymodifying agent.

483. The method of any one of embodiments 457 to 482, further comprisingcombining the plurality of diatom frustule portions with a crosslinkingagent.

484. The method of any one of embodiments 457 to 483, further comprisingcombining the plurality of diatom frustule portions with a flow andlevel agent.

485. The method of any one of embodiments 457 to 484, further comprisingcombining the plurality of diatom frustule portions with at least one ofan adhesion promoting agent, a wetting agent, and a viscosity reducingagent.

486. The method of any one of embodiments 457 to 485, wherein the silvernanostructure comprises at least one of a coating, a nanowire, ananoplate, a dense array of nanoparticles, a nanobelt, and a nanodisk.

487. The method of any one of embodiment 458 to 486, wherein forming thesilver seed layer comprises applying a cyclic heating regimen to a firstsilver contributing component and the plurality of diatom frustuleportions.

488. The method of any one of embodiments 458 to 487, wherein formingthe silver seed layer comprises combining the diatom frustule portionwith a seed layer solution.

489. The method of embodiment 488, wherein the seed layer solutioncomprises the first silver contributing component and a seed layerreducing agent.

490. The method of any one of embodiments 459 to 489, wherein formingthe silver nanostructure comprises combining the diatom frustule portionwith a nanostructure forming reducing agent.

491. The method of embodiment 490, wherein forming the silvernanostructure further comprises heating the diatom frustule portionafter combining the diatom frustule portion with the nanostructureforming reducing agent.

492. The method of any one of embodiments 459 to 491, wherein formingthe silver nanostructure further comprises titrating the diatom frustuleportion with a titration solution comprising a nanostructure formingsolvent and a second silver contributing component.

493. The method of any one of embodiments 457 to 492, wherein theplurality of diatom frustule portions are obtained through a diatomfrustule portion separation process.

494. The method of embodiment 493, wherein the process comprises atleast one of using a surfactant to reduce an agglomeration of aplurality of diatom frustule portions and using a disc stack centrifuge.

495. A conductive silver film comprising:

-   -   a plurality of diatom frustule portions having a silver        nanostructure on a surface of each of the plurality of diatom        frustule portions, the surface comprising a plurality of        perforations.

496. The conductive silver film of embodiment 495, wherein the pluralityof diatom frustule portions comprises a plurality of broken diatomfrustule portion.

497. The conductive silver film of embodiment 495 or 496, wherein theplurality of diatom frustule portions comprises a plurality of diatomfrustule flakes.

498. The conductive silver film of any one of embodiments 495 to 497,wherein at least one of the plurality of perforations comprises adiameter of about 250 nanometers to about 350 nanometers.

499. The conductive silver film of any one of embodiments 495 to 498,wherein the silver nanostructure comprises a thickness of about 10nanometers to about 500 nanometers.

500. The conductive silver film of any one of embodiments 495 to 499,wherein at least one of the plurality of perforations comprises asurface having a silver nanostructure.

501. The conductive silver film of any one of embodiments 495 to 500,wherein at least one of the plurality of perforations comprises asurface having a silver seed layer.

502. The conductive silver film of any one of embodiments 495 to 501,wherein substantially all surfaces of the plurality of diatom frustuleportions comprises a silver nanostructure.

503. The conductive silver film of any one of embodiments 495 to 502,wherein the silver nanostructure comprises at least one of a coating, ananowire, a nanoplate, a dense array of nanoparticles, a nanobelt, and ananodisk.

504. The conductive silver film of any one of embodiments 495 to 503,further comprising a binder resin.

Although this invention has been disclosed in the context of certainembodiments and examples, it will be understood by those skilled in theart that the invention extends beyond the specifically disclosedembodiments to other alternative embodiments and/or uses of theinvention and obvious modifications and equivalents thereof. Inaddition, while several variations of the embodiments of the inventionhave been shown and described in detail, other modifications, which arewithin the scope of this invention, will be readily apparent to those ofskill in the art based upon this disclosure. It is also contemplatedthat various combinations or sub-combinations of the specific featuresand aspects of the embodiments may be made and still fall within thescope of the invention. It should be understood that various featuresand aspects of the disclosed embodiments can be combined with, orsubstituted for, one another in order to form varying modes of theembodiments of the disclosed invention. Thus, it is intended that thescope of the invention herein disclosed should not be limited by theparticular embodiments described above.

The headings provided herein, if any, are for convenience only and donot necessarily affect the scope or meaning of the devices and methodsdisclosed herein.

What is claimed is:
 1. A printed energy storage device comprising: afirst electrode; a second electrode; and a separator between the firstelectrode and the second electrode, at least one of the first electrode,the second electrode, and the separator including frustules.